U.S. patent number 11,331,258 [Application Number 17/267,965] was granted by the patent office on 2022-05-17 for method for dyeing keratinous material, comprising the use of an organosilicon compound, an oligoalkylsiloxane and a dyeing compound.
This patent grant is currently assigned to HENKEL AG & CO. KGAA. The grantee listed for this patent is Henkel AG & Co. KGaA. Invention is credited to Claudia Kolonko, Caroline Kriener, Torsten Lechner, Carsten Mathiaszyk, Marc Nowottny, Juergen Schoepgens, Ulrike Schumacher, Gabriele Weser.
United States Patent |
11,331,258 |
Lechner , et al. |
May 17, 2022 |
Method for dyeing keratinous material, comprising the use of an
organosilicon compound, an oligoalkylsiloxane and a dyeing
compound
Abstract
The subject of the present disclosure is a process for dyeing
keratinous material, in particular human hair, including the
following steps: Application of an agent (a) to the keratinous
material, wherein the agent (a) is at least one organic silicon
compound selected from silanes having one, two or three silicon
atoms, said organic silicon compound including one or more hydroxyl
groups and/or hydrolysable groups per molecule, and said agent (a)
further including at least one oligoalkylsiloxane, and Application
of an agent (b) to the keratinous material, the agent (b) including
at least one colorant compound selected from the group including
pigments and/or direct dyes. A second object of the present
disclosure is a multi-component packaging unit which contains the
two agents (a) and (b) in two separately assembled containers.
Inventors: |
Lechner; Torsten (Langenfeld,
DE), Schoepgens; Juergen (Schwalmtal, DE),
Nowottny; Marc (Moenchengladbach, DE), Weser;
Gabriele (Neuss, DE), Schumacher; Ulrike
(Duesseldorf, DE), Kolonko; Claudia (Remscheid,
DE), Kriener; Caroline (Duesseldorf, DE),
Mathiaszyk; Carsten (Essen, DE) |
Applicant: |
Name |
City |
State |
Country |
Type |
Henkel AG & Co. KGaA |
Duesseldorf |
N/A |
DE |
|
|
Assignee: |
HENKEL AG & CO. KGAA
(Duesseldorf, DE)
|
Family
ID: |
1000006309853 |
Appl.
No.: |
17/267,965 |
Filed: |
May 22, 2019 |
PCT
Filed: |
May 22, 2019 |
PCT No.: |
PCT/EP2019/063192 |
371(c)(1),(2),(4) Date: |
February 11, 2021 |
PCT
Pub. No.: |
WO2020/035186 |
PCT
Pub. Date: |
February 20, 2020 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20210212916 A1 |
Jul 15, 2021 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61Q
5/10 (20130101); A61K 8/585 (20130101) |
Current International
Class: |
A61Q
5/10 (20060101); A61K 8/58 (20060101) |
Field of
Search: |
;8/405 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2168633 |
|
Mar 2010 |
|
EP |
|
2936414 |
|
Apr 2010 |
|
FR |
|
2018115059 |
|
Jun 2018 |
|
WO |
|
Other References
EPO, International Search Report issued in International
Application No. PCT/EP2019/063192, dated Sep. 13, 2019. cited by
applicant .
Arkles et al: "Factors contributing to the stability of
alkoxysilanes in aqueous Solution", Jan. 1992, Silanes and Other
Coupling Agents, p. 91-104, XP007918498. cited by
applicant.
|
Primary Examiner: Elhilo; Eisa B
Attorney, Agent or Firm: Lorenz & Kopf, LLP
Claims
The invention claimed is:
1. A process for dyeing keratinous material comprising the
following steps: applying an agent (a) to the keratinous material,
wherein the agent (a) comprises at least one organic silicon
compound having one, two or three silicon atoms and including one
or more basic chemical functions and one or more hydroxyl groups or
hydrolysable groups per molecule; at least one organic silicon
compound of formula (IV) R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m
(IV), where R.sub.9 represents a C.sub.1-C.sub.12 alkyl group,
R.sub.10 represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl
group, R.sub.11 represents a C.sub.1-C.sub.6 alkyl group k is an
integer from 1 to 3, and m stands for the integer 3 --k, and said
agent (a) further comprising at least one oligoalkylsiloxane, and
applying an agent (b) to the keratinous material, the agent (b)
comprising at least one coloring compound selected from the group
of pigments and direct dyes.
2. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound having one,
two or three silicon atoms and including one or more basic chemical
functions and one or more hydroxyl groups or hydrolysable groups
per molecule, at least one organic silicon compound of formula (I)
and/or (II) R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b
(I), where R.sub.1, R.sub.2 independently represent a hydrogen atom
or a C.sub.1-C.sub.6 alkyl group, L is a linear or branched
divalent C.sub.1-C.sub.2o alkylene group, R.sub.3, R.sub.4
independently of one another represent a C.sub.1-C.sub.6 alkyl
group, a, stands for an integer from 1 to 3, and b is the integer
3-a, and wherein in the organic silicon compound of formula (II)
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-(A''-
)].sub.g-[NR.sub.8-(A''')].sub.h-Si(R.sub.6').sub.d'(OR.sub.5').sub.c'
(II), R5, R5', R5'', R6, R6' and R6'' independently represent a
C.sub.1-C.sub.6 alkyl group, A, A', A'', A''' and A'"'
independently of one another represent a linear or branched
divalent C.sub.1-C.sub.20 alkylene group R7 and R8 independently
represent a hydrogen atom, a C.sub.1-C.sub.6 alkyl group, a hydroxy
C.sub.1-C.sub.6 alkyl group, a C.sub.2-C.sub.6 alkenyl group, an
amino C.sub.1-C.sub.6 alkyl group or a group of formula (III)
(A'''')-Si(R.sub.6'').sub.d''(OR.sub.5'').sub.c'' (III) c, stands
for an integer from 1 to 3, d stands for the integer 3-c, c' stands
for an integer from 1 to 3, d' stands for the integer 3-c', c"
stands for an integer from 1 to 3, d'' stands for the integer
3-c'', e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or
1, h stands for 0 or 1, provided that at least one of e, f, g, and
h is different from 0.
3. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound having one,
two or three silicon atoms and including one or more basic chemical
functions and one or more hydroxyl groups or hydrolysable groups
per molecule, at least one organic silicon compound of formula (I),
R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b (I), where
R.sub.1, R.sub.2 both represent a hydrogen atom, and L represents a
linear, divalent C.sub.1-C.sub.6-alkylene group, R.sub.3, R.sub.4
independently of one another represent a methyl group or an ethyl
group and a stands for the number 3 and b stands for the number
0.
4. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound having one,
two or three silicon atoms and including one or more basic chemical
functions and one or more hydroxyl groups or hydrolysable groups
per molecule, at least one organic silicon compound of formula (I)
selected from the group of (3-Aminopropyl)trimethoxysilane
(3-Aminopropyl)triethoxysilane (2-Aminoethyl)trimethoxysilane
(2-Aminoethyl)triethoxysilane
(3-Dimethylaminopropyl)trimethoxysilane
(3-Dimethylaminopropyl)triethoxysilane
(2-Dimethylaminoethyl)trimethoxysilane and
(2-Dimethylaminoethyl)triethoxysilane.
5. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound having one,
two or three silicon atoms and including one or more basic chemical
functions and one or more hydroxyl groups or hydrolysable groups
per molecule, at least one organic silicon compound of the formula
(II),
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-(A''-
)].sub.g-[NR.sub.8-(A'')].sub.h-Si(R.sub.6).sub.d'(OR.sub.5).sub.c'
(II) where e and f both stand for the number 1, g and h both stand
for the number 0, A and A' independently represent a linear,
divalent C.sub.1-C.sub.6 alkylene group and R7 represents a
hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl
group, a 2-aminoethyl group or a group of formula (III).
6. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound having one,
two or three silicon atoms and including one or more basic chemical
functions and one or more hydroxyl groups or hydrolysable groups
per molecule, at least one organic silicon compound of the formula
(II) which is selected from the group of
3-(trimethoxysilyl)-N[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N[3-(triethoxysilyl)propyl]-1-propanamine
N-methyl-3-(trimethoxysilyl)-N43-(trimethoxysilyl)propyl]-1-propanamine
N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
2-[bis[3-(triethoxysilyl)propyl]amino]ethanol
3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine
N1,Ni -bis [3-(trimethoxysilyl)propyl]-1,2-ethanediamine, N1,Ni -bi
s [3-(triethoxysilyl)propyl]-1,2-ethanediamine, N,N-bis
[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or N,N-bis
[3-(triethoxysilyl)propyl]-2-propen-1-amine.
7. The process according to claim 1, wherein the agent (a)
comprises as the at least one organic silicon compound of formula
(IV) at least one organic silicon compound selected from the group
of Methyltrimethoxysilane Methyltriethoxysilane
Ethyltrimethoxysilane Ethyltriethoxysilane Octyltrimethoxysilane
Octyltriethoxysilane Dodecyltrimethoxysilane and/or
Dodecyltriethoxysilane.
8. The process according to claim 1, wherein the agent (a)
comprises-- based on the total weight of the agent (a)-- the
organic silicon compounds in a total amount of 0.1 to 20.0% by
weight.
9. The process according to claim 2, wherein the agent (a)
comprises-- based on the total weight of the agent (a)-- the at
least one organic silicon compounds of the formula (I) and/or (II)
in a total amount of from about 0.1 to about 10.0% by weight.
10. The process according to claim 1, wherein the agent (a)
comprises-- based on the total weight of the agent (a)-- the at
least one organic silicon compounds of the formula (IV) in a total
amount of from about 0.1 to about 20.0% by weight.
11. The process according to claim 1, wherein the agent (a)
comprises as the at least one oligoalkylsiloxane, at least one
linear and/or cyclic oligoalkylsiloxane.
12. The process according to claim 1, wherein the agent (a)
comprises as the at least one oligoalkylsiloxane, at least one
oligoalkylsiloxane of the formula (V) and/or (VI), ##STR00010##
where z is an integer from 0 to 10, ##STR00011## where y is an
integer from 1 to 5.
13. The process according to claim 1, wherein the agent (a)
comprises as the at least one oligoalkylsiloxane, at least one
oligoalkylsiloxane selected from the group of hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and
decamethylcyclopentasiloxane.
14. The process according to claim 1, wherein the agent (a)
comprises-- based on the total weight of the agent (a)-- the one or
more oligoalkylsiloxanes in a total amount of from about 0.1 to
about 25.0% by weight.
15. The process according to claim 1, wherein the agent (b)
comprises as the at least one coloring compound, at least one
coloring compound chosen from the group of pigments selected from
the group of colored metal oxides, metal hydroxides, metal oxide
hydrates, silicates, metal sulphides, complex metal cyanides, metal
sulphates, bronze pigments and from colored pigments based on mica
or mica which are coated with at least one metal oxide and/or one
metal oxychloride.
16. The process according to claim 1, wherein the agent (b)
comprises as the at least one coloring compound, at least one
coloring compound chosen from the group of organic pigments which
is selected from the group of carmine, quinacridone,
phthalocyanine, sorghum, blue pigments having the color index
numbers Cl 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI 74160,
yellow pigments having the color index numbers CI 11680, CI 11710,
CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000, CI
47005, green pigments with Color Index numbers CI 61565, CI 61570,
CI 74260, orange pigments with Color Index numbers CI 11725, CI
15510, CI 45370, CI 71105, red pigments with Color Index numbers CI
12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700, CI 15525,
CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI 15865, CI
15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000, CI 73360,
CI 73915 and CI 75470.
17. The process according to claim 1, wherein the agent (b)
comprises as the at least one coloring compound, at least one
direct dye which is selected from the group of anionic, cationic,
and nonionic direct dyes.
18. The process according to claim 1, wherein the agent (b)
comprises as the at least one coloring compound, at least one
anionic direct dye selected from the group of Acid Yellow 1, Acid
Yellow 3, Acid Yellow 9, Acid Yellow 17, Acid Yellow 23, Acid
Yellow 36, Acid Yellow 121, Acid Orange 6, Acid Orange 7, Acid
Orange 10, Acid Orange 11, Acid Orange 15, Acid Orange 20, Acid
Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid Red 33, Acid
Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid Red 87, Acid
Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid Violet 43,
Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue 3, Acid Blue
7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue 74, Acid
Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid Green 22,
Acid Green 25, Acid Green 50, Acid Black 1, Acid Black 52, Food
Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5, D&C
Orange 10, D&C Orange 11, D&C Red 21, D&C Red 27,
D&C Red 33, D&C Violet 2 and D&C Brown 1.
Description
CROSS-REFERENCE TO RELATED APPLICATION
This application is a U.S. National-Stage entry under 35 U.S.C.
.sctn. 371 based on International Application No.
PCT/EP2019/063192, filed May 22, 2019, which was published under
PCT Article 21(2) and which claims priority to German Application
No. 10 2018 213 813.3, filed Aug. 16, 2018, which are all hereby
incorporated in their entirety by reference.
TECHNICAL FIELD
The subject of the present application is a process for dyeing
keratinous material, especially human hair, which includes the
application of at least two different agents (a) and (b). The agent
(a) contains at least one organic silicon compound and at least one
oligoalkylsiloxane. The agent (b) includes at least one colorant
compound selected from the group including pigments and/or direct
dyes.
The second subject-matter of this application is a multi-component
packaging unit (kit-of-parts) for coloring keratinous material, in
particular human hair, which includes the agents (a) and (b)
separately packaged in two different containers.
BACKGROUND
Changing the shape and color of keratinous material, especially
human hair, is an important area of modern cosmetics. To change the
hair color, the expert knows various coloring systems depending on
the coloring requirements. Oxidation dyes are usually used for
permanent, intensive dyeing's with good fastness properties and
good grey coverage. Such colorants contain oxidation dye
precursors, so-called developer components and coupler components,
which, under the influence of oxidizing agents such as hydrogen
peroxide, form the actual dyes among themselves. Oxidation dyes are
exemplified by very long-lasting dyeing results.
When direct dyes are used, ready-made dyes diffuse from the
colorant into the hair fiber. Compared to oxidative hair dyeing,
the dyeing's obtained with direct dyes have a shorter shelf life
and quicker wash ability. Dyeing with direct dyes usually remain on
the hair for a period of between about 5 and about 20 washes.
The use of color pigments is known for short-term color changes on
the hair and/or skin. Color pigments are generally understood to be
insoluble, coloring substances. These are present undissolved in
the dye formulation in the form of small particles and are only
deposited from the outside on the hair fibers and/or the skin
surface. Therefore, they can usually be removed again without
residue by a few washes with detergents containing surfactants.
Various products of this type are available on the market under the
name hair mascara.
If the user wants particularly long-lasting dyeing's, the use of
oxidative dyes has so far been his only option. However, despite
numerous optimization attempts, an unpleasant ammonia or amine odor
cannot be completely avoided in oxidative hair dyeing. The hair
damage still associated with the use of oxidative dyes also has a
negative effect on the user's hair. A continuing challenge is
therefore the search for alternative, high-performance dyeing
processes.
EP 2168633 B1 deals with the task of producing long-lasting hair
colorations using pigments. The paper teaches that when a
combination of pigment, organic silicon compound, hydrophobic
polymer and a solvent is used on hair, it is possible to create
colorations that are said to be particularly resistant to
shampooing. For example, 3-aminopropyl-triethoxysilane was used as
organic silicon compound.
In WO 2018/115059 A1 a dyeing process is described, which runs in
several steps. One step involves the application of an
organosilane, and another step involves the application of a
direct-pull dye to the hair. This process is also used to achieve
dyeing's with good wash fastness properties. The silanes used in
this writing are for example 3-aminopropyltriethxoysilane and
methyltrimethoxysilane.
In the dyeing processes of EP 2168633 B1 and WO 2018/115059 A1,
organosilicon compounds from the group of silanes are used, the
molecular structure of these silanes including at least one hydroxy
group and/or hydrolysable group. Due to the presence of hydroxy
groups or hydrolysable groups, silanes are reactive substances that
hydrolyze or oligomerize or polymerize in the presence of water.
When applied to the keratin material, the oligomerization or
polymerization of the silanes initiated by the presence of water
ultimately leads to the formation of a film which fixes the
coloring compounds and thus produces very long-lasting
colorations.
A closer examination of the dyeing processes disclosed in EP
2168633 B1 and WO 2018/115059 A1 has shown that the timing of film
formation is essential for the quality of the color result. It has
been found that optimum dyeing results can only be obtained if the
formation of the film is precisely matched to the time of
application.
If the oligomerization or polymerization of the silanes takes place
too early or too quickly, large conglomerates already form in the
container. In this case, the formulation containing the silanes
already gels in the vessel in which it is provided. The production
of intensive or long-lasting colorings is no longer possible this
way.
On the other hand, too slow oligomerization or polymerization is
also disadvantageous about the color result, because if the film
cannot form from the keratinous material with sufficient speed, the
fixation of the coloring compounds on the keratin also does not
take place or only to an incomplete extent. The consequence of too
slow polymerization is therefore too weak color intensities and a
much too fast wash-out of the coloring.
A major challenge in dyeing processes with silanes therefore
remains the matching of the polymerization rate to the dyeing
process. To a first approximation, there is a direct correlation
between the speed of polymerization and the water content of the
colorant. The higher the water content, the faster the silanes
polymerise.
However, further dyeing tests have shown that the sensitivity of
the silanes to water is so high that even traces of atmospheric
moisture can initiate premature hydrolysis. If the silanes are
decanted without a protective gas, for example, even brief contact
with moisture from the air is sufficient to initiate hydrolysis
that begins far too early. The storage stability of the containers
produced in humid air is therefore poor.
BRIEF SUMMARY
The purpose of the present inventive efforts was to provide a
dyeing system with fastness properties comparable to those of
oxidative dyeing. Wash fastness properties should be outstanding,
but the use of oxidation dye precursors normally used for this
purpose should be avoided. A technology was sought that would make
it possible to fix colorant compounds known from the prior art
(such as pigments or direct-acting dyes) to the hair in an
extremely durable manner. The production of the dyes should be
inexpensive and the dyes themselves should have particularly good
storage stability. When using the agents in a dyeing process,
consistently good color results should be achievable regardless of
the conditions prevailing during production and application (such
as humidity and temperature).
Surprisingly, it has now turned out that the above-mentioned task
can be excellently solved if keratinous materials, especially hair,
are dyed using a procedure in which at least two agents (a) and (b)
are applied to the keratinous materials (hair). In this case, the
agent (a) contains at least one organic silicon compound (from the
group of reactive silanes) and additionally at least one
oligoalkylsiloxane. The agent (b) contains at least one coloring
compound from the group of pigments and direct dyes. When both
agents (a) and (b) were used in a dyeing process, keratinous fibers
could be dyed to a consistently high color intensity regardless of
the conditions prevailing during manufacture and application. In
addition, the wash fastness of the hair dyed with (a) and (b) was
excellent.
DETAILED DESCRIPTION
The following detailed description is merely exemplary in nature
and is not intended to limit the disclosure or the application and
uses of the subject matter as described herein. Furthermore, there
is no intention to be bound by any theory presented in the
preceding background or the following detailed description.
A first object of the present disclosure is a method for coloring
keratinous material, in particular human hair, including the
following steps: Application of an agent (a) to the keratinous
material, wherein the agent (a) contains at least one organic
silicon compound selected from silanes having one, two or three
silicon atoms, wherein the organic silicon compound includes one or
more hydroxyl groups and/or hydrolysable groups per molecule, and
wherein the agent (a) further contains at least one
oligoalkylsiloxane, and Application of an agent (b) to the
keratinous material, the agent (b) containing at least one coloring
compound from the group of pigments and/or direct dyes. Keratinic
Material
Keratinous material includes hair, skin, nails (such as fingernails
and/or toenails). Wool, furs, and feathers also fall under the
definition of keratinous material. Suitably, keratinous material is
understood to be human hair, human skin, and human nails,
especially fingernails and toenails. Keratinous material is
understood to be human hair.
Agent (a) and (b)
In the procedure as contemplated herein, agents (a) and (b) are
applied to the keratinous material, in particular human hair. The
two means (a) and (b) are different.
In other words, a first subject of the present disclosure is a
process for dyeing keratinous material, in particular human hair,
including the following steps: Application of an agent (a) to the
keratinous material, wherein the agent (a) contains at least one
organic silicon compound selected from silanes having one, two or
three silicon atoms, wherein the organic silicon compound includes
one or more hydroxyl groups and/or hydrolysable groups per
molecule, and wherein the agent (a) further contains at least one
oligoalkylsiloxane, and Application of an agent (b) to the
keratinous material, the agent (b) containing at least one coloring
compound from the group of pigments and/or direct dyes, the two
agents (a) and (b) being different from one another. Agent (a)
As a first ingredient essential to the present disclosure, the
composition (a) contains at least one organic silicon compound
selected from silanes having one, two or three silicon atoms, the
organic silicon compound including one or more hydroxyl groups
and/or hydrolysable groups per molecule.
As already described, the organic silicon compounds or organic
silanes contained in agent (a) are reactive compounds.
Composition (a) contains the organic silicon compound(s), in
particular the organic silane(s), in a cosmetic carrier which may
be hydrated, low in water or anhydrous. In addition, the cosmetic
carrier can be liquid, gel-like, creamy, powdery, or even solid
(e.g., in the form of a tablet or pellet). Suitably, the cosmetic
carrier of the product (a) is an aqueous or aqueous-alcoholic
carrier. To hair coloration, such carriers are, for example,
creams, emulsions, gels, or surfactant-containing foaming
solutions, such as shampoos, foam aerosols, foam formulations or
other preparations suitable for application to the hair.
The cosmetic carrier suitably contains water, which means that the
carrier contains at least about 2% by weight of water based on its
weight. Suitably, the water content is above about 5 wt. %, further
suitably above about 10 wt. % still further suitably above about 15
wt. %. The cosmetic carrier can also be aqueous-alcoholic.
Aqueous/alcoholic solutions in the context of the present
disclosure are aqueous solutions containing from about 2 to about
70% by weight of a C.sub.1-C.sub.4 alcohol, more particularly
ethanol or isopropanol. The agents as contemplated herein may
additionally contain other organic solvents, such as methoxy
butanol, benzyl alcohol, ethyl diglycol or 1,2-propylene glycol.
Exemplary are all water-soluble organic solvents.
The term "dyeing agent" is used in the context of this present
disclosure for a coloration of the keratin material, of the hair,
caused using pigments and/or direct dyes. In this staining process,
the colorant compounds are deposited in a particularly homogeneous
and smooth film on the surface of the keratin material or diffuse
into the keratin fiber. The film is formed in situ by
oligomerization or polymerization of the organic silicon
compound(s), as well as by the interaction of organic silicon
compound with the colorant compound.
Organic Silicon Compounds
As the first ingredient essential to the present disclosure, the
agent (a) contains at least one organic silicon compound. Organic
silicon compounds as contemplated herein are selected from silanes
with one, two or three silicon atoms.
Organic silicon compounds, alternatively called organosilicon
compounds, are compounds which either have a direct silicon-carbon
bond (Si--C) or in which the carbon is bonded to the silicon atom
via an oxygen, nitrogen, or sulfur atom. The organic silicon
compounds as contemplated herein are compounds containing one to
three silicon atoms. Organic silicon compounds suitably contain one
or two silicon atoms.
According to IUPAC rules, the term silane chemical compounds based
on a silicon skeleton and hydrogen. In organic silanes, the
hydrogen atoms are completely or partially replaced by organic
groups such as (substituted) alkyl groups and/or alkoxy groups. In
organic silanes, some of the hydrogen atoms may also be replaced by
hydroxy groups.
The agent (a) contains at least one organic silicon compound
selected from silanes having one, two or three silicon atoms,
wherein the organic silicon compound includes one or more hydroxyl
groups or hydrolysable groups per molecule.
In a suitable embodiment, a method as contemplated herein is
exemplified by the application of an agent (a) to the keratinous
material, said agent (a) including at least one organic silicon
compound selected from silanes having one, two or three silicon
atoms, said organic silicon compound further including one or more
basic chemical functions and one or more hydroxyl groups or
hydrolysable groups per molecule.
This basic group can be, for example, an amino group, an alkylamino
group or a dialkylamino group, which is suitably connected to a
silicon atom via a linker. The basic group is suitably an amino
group, a C.sub.1-C.sub.6 alkylamino group or a
di(C.sub.1-C.sub.6)alkylamino group.
The hydrolysable group(s) is (are) suitably a C.sub.1-C.sub.6
alkoxy group, especially an ethoxy group or a methoxy group. It is
exemplary when the hydrolysable group is directly bonded to the
silicon atom. For example, if the hydrolysable group is an ethoxy
group, the organic silicon compound suitably contains a structural
unit R'R''R'''Si--O--CH2-CH3. The residues R', R'' and R'''
represent the three remaining free valences of the silicon
atom.
A suitable method as contemplated herein the composition includes
(a) at least one organic silicon compound selected from silanes
having one, two or three silicon atoms, the organic silicon
compound suitably including one or more basic chemical functions
and one or more hydroxyl groups or hydrolysable groups per
molecule.
Particularly good results could be obtained if the agent as
contemplated herein (a) contains at least one organic silicon
compound of formula (I) and/or (II).
The compounds of formulae (I) and (II) are organic silicon
compounds selected from silanes having one, two or three silicon
atoms, the organic silicon compound including one or more hydroxyl
groups and/or hydrolysable groups per molecule.
In another very suitable embodiment, a process as contemplated
herein an agent (a) is applied to the keratinous material (or human
hair), the agent (a) including at least one organic silicon
compound (a) of the formula (I) and/or (II),
R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b (I),
where R.sub.1, R.sub.2 independently represent a hydrogen atom or a
C.sub.1-C.sub.6 alkyl group, L is a linear or branched divalent
C.sub.1-C.sub.20 alkylene group, R.sub.3 represents a hydrogen atom
or a C.sub.1-C.sub.6 alkyl group, R.sub.4 represents a
C.sub.1-C.sub.6 alkyl group a, stands for an integer from 1 to 3,
and b stands for the integer 3-a,
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-
-(A'')].sub.g-[NR.sub.8-(A''')].sub.h-Si(R.sub.6').sub.d'(OR.sub.5').sub.c-
' (II),
where R.sub.5, R.sub.5', R.sub.5'' independently represent a
hydrogen atom or a C.sub.1-C.sub.6 alkyl group, R.sub.6, R.sub.6'
and R.sub.6'' independently represent a C.sub.1-C.sub.6 alkyl
group, A, A', A'', A''' and A'''' independently of one another
represent a linear or branched divalent C.sub.1-C.sub.20 alkylene
group R.sub.7 and R.sub.8 independently represent a hydrogen atom,
a C.sub.1-C.sub.6 alkyl group, a hydroxy C.sub.1-C.sub.6 alkyl
group, a C.sub.2-C.sub.6 alkenyl group, an amino C.sub.1-C.sub.6
alkyl group or a group of formula (III)
-(A'''')-Si(R.sub.6'').sub.d''(OR.sub.5'').sub.c'' (III), c, stands
for an integer from 1 to 3, d stands for the integer 3-c, c' stands
for an integer from 1 to 3, d' stands for the integer 3-c', c''
stands for an integer from 1 to 3, d'' stands for the integer
3-c'', e stands for 0 or 1, f stands for 0 or 1, g stands for 0 or
1, h stands for 0 or 1, provided that at least one of e, f, g, and
h is different from 0.
The substituents R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5,
R.sub.5', R.sub.5'', R.sub.6, R.sub.6', R.sub.6'', R.sub.7,
R.sub.8, L, A, A', A'', A'''' and A'''' in the compounds of formula
(I) and (II) are explained below as examples: Examples of a
C.sub.1-C.sub.6 alkyl group are the groups methyl, ethyl, propyl,
isopropyl, n-butyl, s-butyl, and t-butyl, n-pentyl and n-hexyl.
Propyl, ethyl, and methyl are exemplary alkyl radicals. Examples of
a C.sub.2-C.sub.6 alkenyl group are vinyl, allyl, but-2-enyl,
but-3-enyl and isobutenyl, exemplary C.sub.2-C.sub.6 alkenyl
radicals are vinyl and allyl. Exemplary examples of a hydroxy
C.sub.1-C.sub.6 alkyl group are a hydroxymethyl, a 2-hydroxyethyl,
a 2-hydroxypropyl, a 3-hydroxypropyl, a 4-hydroxybutyl group, a
5-hydroxypentyl and a 6-hydroxyhexyl group; a 2-hydroxyethyl group
is suitable. Examples of an amino C.sub.1-C.sub.6 alkyl group are
the aminomethyl group, the 2-aminoethyl group, the 3-aminopropyl
group. The 2-aminoethyl group is suitable. Examples of a linear
divalent C.sub.1-C.sub.20 alkylene group include the methylene
group (--CH.sub.2), the ethylene group (--CH.sub.2--CH.sub.2--),
the propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--) and the
butylene group (--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2). The
propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--) is suitable.
From a chain length of 3 C atoms, divalent alkylene groups can also
be branched. Examples of branched divalent C.sub.3-C.sub.20
alkylene groups are (--CH.sub.2--CH(CH.sub.3)--) and
(--CH.sub.2--CH(CH.sub.3)--CH.sub.2--).
In the organic silicon compounds of the formula (I)
R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b (I), the
radicals R.sub.1 and R.sub.2 independently of one another represent
a hydrogen atom or a C.sub.1-C.sub.6 alkyl group. In particular,
the radicals R.sub.1 and R.sub.2 both represent a hydrogen
atom.
In the middle part of the organic silicon compound is the
structural unit or the linker -L- which stands for a linear or
branched, divalent C.sub.1-C.sub.20 alkylene group.
Suitably -L- stands for a linear, divalent C.sub.1-C.sub.20
alkylene group. Further suitably -L-stands for a linear divalent
C.sub.1-C.sub.6 alkylene group. Suitable -L- stands for a methylene
group (--CH.sub.2--), an ethylene group (--CH.sub.2--CH.sub.2--),
propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--) or butylene
(--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--). L stands for a
propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--)
The organic silicon compounds of formula (I)
R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b (I), one end of
each carries the silicon-containing group
--Si(OR.sub.3).sub.a(R.sub.4).sub.b
In the terminal structural unit
--Si(OR.sub.3).sub.a(R.sub.4).sub.b, R.sub.3 is hydrogen or
C.sub.1-C.sub.6 alkyl group, and R.sub.4 is C.sub.1-C.sub.6 alkyl
group. R.sub.3 and R.sub.4 independently of each other represent a
methyl group or an ethyl group.
Here a stands for an integer from 1 to 3, and b stands for the
integer 3-a. If a stands for the number 3, then b is equal to 0. If
a stands for the number 2, then b is equal to 1. If a stands for
the number 1, then b is equal to 2.
Dyes with the best wash fastness values could be obtained if the
pretreatment agent contains at least one organic silicon compound
corresponding to formula (I): in which R.sub.3, R.sub.4
independently of one another represent a methyl group or an ethyl
group.
Furthermore, dyeing's with the best wash fastness properties could
be obtained if the agent as contemplated herein contains at least
one organic silicon compound of formula (I) in which the radical a
represents the number 3. In this case the rest b stands for the
number 0.
In another exemplary embodiment, an agent as contemplated herein
contains (a) at least one organic silicon compound of formula
(I),
where R.sub.3, R.sub.4 independently of one another represent a
methyl group or an ethyl group and a stands for the number 3 and b
stands for the number 0.
In another exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of
formula (I), R.sub.1R.sub.2N-L-Si(OR.sub.3).sub.a(R.sub.4).sub.b
(I), where R.sub.1, R.sub.2 both represent a hydrogen atom, and L
represents a linear, divalent C.sub.1-C.sub.6-alkylene group,
suitably a propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--) or an
ethylene group (--CH.sub.2--CH.sub.2--), R.sub.3 represents a
hydrogen atom, an ethyl group, or a methyl group, R.sub.4
represents a methyl group or an ethyl group, a stands for the
number 3 and b stands for the number 0.
Organic silicon compounds of the formula (I) which are particularly
suitable for solving the problem as contemplated herein are.
##STR00001##
In a further exemplary embodiment, a process as contemplated herein
the agent (a) includes at least one organic silicon compound of
formula (I) selected from the group including
(3-Aminopropyl)triethoxysilan (3-Aminopropyl)trimethoxysilane
1-(3-Aminopropyl)silantriol (2-Aminoethyl)triethoxysilan
(2-Aminoethyl)trimethoxysilane 1-(2-Aminoethyl)silantriol
(3-Dimethylaminopropyl)triethoxysilan
(3-Dimethylaminopropyl)trimethoxysilane
1-(3-Dimethylaminopropyl)silantriol
(2-Dimethylaminoethyl)triethoxysilan.
(2-Dimethylaminoethyl)trimethoxysilane and/or
1-(2-Dimethylaminoethyl)silantriol.
The organic silicon compound of formula (I) is commercially
available. (3-aminopropyl)trimethoxysilane, for example, can be
purchased from Sigma-Aldrich. Also (3-aminopropyl)triethoxysilane
is commercially available from Sigma-Aldrich.
In a further version, the present disclosure contains at least one
organic silicon compound of formula (II)
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-(A''-
)].sub.g-[NR.sub.8-(A''')].sub.h-Si(R.sub.6').sub.d'(OR.sub.5').sub.c'
(II).
The organosilicon compounds of formula (II) as contemplated herein
each carry the silicon-containing groups
(R.sub.5O).sub.c(R.sub.6).sub.dSi-- and
--Si(R.sub.6').sub.d'(OR.sub.5').sub.c' at both ends.
In the central part of the molecule of formula (II) there are the
groups -(A).sub.e- and --[NR.sub.7-(A')].sub.f-
and [O-(A'')].sub.g- and --[NR.sub.8-(A''')].sub.h-. Here, each of
the radicals e, f, g, and h can independently of one another stand
for the number 0 or 1, with the proviso that at least one of the
radicals e, f, g, and h is different from 0. In other words, an
organic silicon compound of formula (II) as contemplated herein
contains at least one grouping from the group including -(A)- and
--[NR.sub.7-(A')]- and --[O-(A'')]- and --[NR.sub.8-(A''')]-.
In the two terminal structural units
(R.sub.5O).sub.c(R.sub.6).sub.dSi-- and
--Si(R.sub.6').sub.d'(OR.sub.5').sub.c', the radicals R5, R5', R5''
independently of one another represent a hydrogen atom or a
C.sub.1-C.sub.6 alkyl group. The radicals R6, R6' and R6''
independently represent a C.sub.1-C.sub.6 alkyl group.
Here a stands for an integer from 1 to 3, and d stands for the
integer 3-c. If c stands for the number 3, then d is equal to 0. If
c stands for the number 2, then d is equal to 1. If c stands for
the number 1, then d is equal to 2.
Analogously c' stands for a whole number from 1 to 3, and d' stands
for the whole number 3-c'. If c' stands for the number 3, then d'
is 0. If c' stands for the number 2, then d' is 1. If c' stands for
the number 1, then d' is 2.
Dyeing's with the best wash fastness values could be obtained if
the residues c and c' both stand for the number 3. In this case d
and d' both stand for the number 0.
In another exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of
formula (II),
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-(A''-
)].sub.g-[NR.sub.8-(A''')].sub.h-Si(R.sub.6').sub.d'(OR.sub.5').sub.c'
(II), where R5 and R5' independently represent a methyl group or an
ethyl group, c and c' both stand for the number 3 and d and d' both
stand for the number 0.
If c and c' are both the number 3 and d and d' are both the number
0, the organic silicon compound of the present disclosure
corresponds to formula (Ha)
(R.sub.5O).sub.3Si-(A).sub.e-[NR.sub.7-(A')].sub.f[O-(A'')].sub.g-[N-
R.sub.8-(A''')].sub.h-Si(OR.sub.5').sub.3 (IIa).
The radicals e, f, g, and h can independently stand for the number
0 or 1, whereby at least one radical from e, f, g, and h is
different from zero. The abbreviations e, f, g, and h thus define
which of the groupings -(A).sub.e- and [NR.sub.7-(A')].sub.f- and
--[O-(A'')].sub.g and --[NR.sub.8-(A''')].sub.h-are in the middle
part of the organic silicon compound of formula (II).
In this context, the presence of certain groupings has proved to be
particularly beneficial in terms of increasing washability.
Particularly good results were obtained when at least two of the
residues e, f, g, and h stand for the number 1. Especially
exemplary e and f both stand for the number 1. Furthermore, g and h
both stand for the number 0.
If e and f both stand for the number 1 and g and h both stand for
the number 0, the organic silicon compound as contemplated herein
corresponds to formula (IIb)
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A)-[NR.sub.7-(A')]-Si(R.sub.6').sub.d'-
(OR.sub.5').sub.c' (IIb).
The radicals A, A', A'', A''' and A'''' independently represent a
linear or branched divalent C.sub.1-C.sub.20 alkylene group.
Suitably the radicals A, A', A'', A''' and A'''' independently of
one another represent a linear, divalent C.sub.1-C.sub.20 alkylene
group. Further suitably the radicals A, A', A'', A''' and A''''
independently represent a linear divalent C.sub.1-C.sub.6 alkylene
group. In particular, the radicals A, A', A'', A''' and A''''
independently of one another represent a methylene group
(--CH.sub.2--), an ethylene group (--CH.sub.2--CH.sub.2--), a
propylene group (--CH.sub.2--CH.sub.2--CH.sub.2--) or a butylene
group (--CH.sub.2--CH.sub.2--CH.sub.2--CH.sub.2--). In particular,
the residues A, A', A'', A''' and A'''' stand for a propylene group
(--CH.sub.2--CH.sub.2--CH.sub.2--).
If the radical f represents the number 1, then the organic silicon
compound of formula (II) as contemplated herein contains a
structural grouping --[NR.sub.7-(A')]-.
If the radical f represents the number 1, then the organic silicon
compound of formula (II) as contemplated herein contains a
structural grouping --[NR.sub.8-(A''')]-.
Wherein R.sub.7 and R.sub.8 independently represent a hydrogen
atom, a C.sub.1-C.sub.6 alkyl group, a hydroxy-C.sub.1-C.sub.6
alkyl group, a C.sub.2-C.sub.6 alkenyl group, an
amino-C.sub.1-C.sub.6 alkyl group or a group of the formula (III)
-(A'''')-Si(R.sub.6'').sub.d''(OR.sub.5'').sub.c'' (III).
Very suitably the radicals R7 and R8 independently of one another
represent a hydrogen atom, a methyl group, a 2-hydroxyethyl group,
a 2-alkenyl group, a 2-aminoethyl group or a grouping of the
formula (III).
If the radical f represents the number 1 and the radical h
represents the number 0, the organic silicon compound as
contemplated herein contains the grouping [NR.sub.7-(A')] but not
the grouping --[NR.sub.8-(A''')]. If the radical R7 now stands for
a grouping of the formula (III), the pretreatment agent (a)
contains an organic silicon compound with 3 reactive silane
groups.
In another exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of
formula (II),
(R.sub.5O).sub.c(R.sub.6).sub.dSi-(A).sub.e-[NR.sub.7-(A')].sub.f-[O-(A''-
)].sub.g-[NR.sub.8-(A''')].sub.h-Si(R.sub.6').sub.d'(OR.sub.5').sub.c'
(II), where e and f both stand for the number 1, g and h both stand
for the number 0, A and A' independently represent a linear,
divalent C.sub.1-C.sub.6 alkylene group and R7 represents a
hydrogen atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl
group, a 2-aminoethyl group or a group of formula (III).
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of the
formula (II), where e and f both stand for the number 1, g and h
both stand for the number 0, A and A' independently of one another
represent a methylene group (--CH.sub.2--), an ethylene group
(--CH.sub.2--CH.sub.2--) or a propylene group
(--CH.sub.2--CH.sub.2--CH.sub.2), and R7 represents a hydrogen
atom, a methyl group, a 2-hydroxyethyl group, a 2-alkenyl group, a
2-aminoethyl group or a group of formula (III).
Organic silicon compounds of the formula (II) which are well suited
for solving the problem as contemplated herein are.
##STR00002## ##STR00003##
The organic silicon compounds of formula (II) are commercially
available.
Bis(trimethoxysilylpropyl)amines with the CAS number 82985-35-1 can
be purchased from Sigma-Aldrich.
Bis[3-(triethoxysilyl)propyl]amines with the CAS number 13497-18-2
can be purchased from Sigma-Aldrich, for example.
N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
is alternatively referred to as
bis(3-trimethoxysilylpropyl)-N-methylamine and can be purchased
commercially from Sigma-Aldrich or Fluorochem.
3-(triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine
with the CAS number 18784-74-2 can be purchased for example from
Fluorochem or Sigma-Aldrich.
In another exemplary embodiment, an agent as contemplated herein
contains (a) at least one organic silicon compound of formula (II)
selected from the group including
3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
N-methyl-3-(trimethoxysilyl)-N-[3-(trimethoxysilyl)propyl]-1-propanamine
N-Methyl-3-(triethoxysilyl)-N-[3-(triethoxysilyl)propyl]-1-propanamine
2-[Bis[3-(trimethoxysilyl)propyl]amino]-ethanol
2-[bis[3-(triethoxysilyl)propyl]amino]ethanol
3-(Trimethoxysilyl)-N,N-bis[3-(trimethoxysilyl)propyl]-1-propanamine
3-(Triethoxysilyl)-N,N-bis[3-(triethoxysilyl)propyl]-1-propanamine
N1,N1-bis[3-(trimethoxysilyl)propyl]-1,2-ethanediamine,
N1,N1-bis[3-(triethoxysilyl)propyl]-1,2-ethanediamine,
N,N-bis[3-(trimethoxysilyl)propyl]-2-propen-1-amine and/or
N,N-bis[3-(triethoxysilyl)propyl]-2-propen-1-amine
In further dyeing tests, it has also proved to be particularly
advantageous if the agent used on the keratinous material in the
process as contemplated herein (a) contains at least one organic
silicon compound of formula (IV)
R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m (IV).
The compounds of formula (IV) are organic silicon compounds
selected from silanes having one, two or three silicon atoms, the
organic silicon compound including one or more hydroxyl groups
and/or hydrolysable groups per molecule.
The organic silicon compound(s) of formula (IV) may also be called
a silane of the alkyl-alkoxy-silane or alkyl-hydroxy-silane type,
R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m (IV), where R.sub.9
represents a C.sub.1-C.sub.12, alkyl group, R.sub.10 represents a
hydrogen atom or a C.sub.1-C.sub.6 alkyl group, R.sub.11 represents
a C.sub.1-C.sub.6 alkyl group k is an integer from 1 to 3, and m
stands for the integer 3-k.
In another exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of
formula (IV). R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m (IV),
where R.sub.9 represents a C.sub.1-C.sub.12 alkyl group, R.sub.10
represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl group,
R.sub.11 represents a C.sub.1-C.sub.6 alkyl group k is an integer
from 1 to 3, and m stands for the integer 3-k.
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains, in addition to the organic silicon
compound(s) of formula (I), at least one further organic silicon
compound of formula (IV) R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m
(IV), where R.sub.9 represents a C.sub.1-C.sub.12 alkyl group,
R.sub.10 represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl
group, R.sub.11 represents a C.sub.1-C.sub.6 alkyl group k is an
integer from 1 to 3, and m stands for the integer 3-k.
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains, in addition to the organic silicon compound
or compounds of the formula (II), at least one further organic
silicon compound of the formula (IV)
R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m (IV), where R.sub.9
represents a C.sub.1-C.sub.12 alkyl group, R.sub.10 represents a
hydrogen atom or a C.sub.1-C.sub.6 alkyl group, R.sub.11 represents
a C.sub.1-C.sub.6 alkyl group k is an integer from 1 to 3, and m
stands for the integer 3-k.
In a further exemplary embodiment, a process as contemplated herein
the composition contains (a) in addition to the organic silicon
compound(s) of formula (I) and/or (II) at least one further organic
silicon compound of formula (IV)
R.sub.9Si(OR.sub.10).sub.k(R.sub.11).sub.m (IV), where R.sub.9
represents a C.sub.1-C.sub.12 alkyl group, R.sub.10 represents a
hydrogen atom or a C.sub.1-C.sub.6 alkyl group, R.sub.11 represents
a C.sub.1-C.sub.6 alkyl group k is an integer from 1 to 3, and m
stands for the integer 3-k.
In the organic silicon compounds of formula (IV), the radical
R.sub.9 represents a C.sub.1-C.sub.12 alkyl group. This
C.sub.1-C.sub.12 alkyl group is saturated and can be linear or
branched. Suitably R9 stands for a linear C.sub.1-C.sub.8 alkyl
group. Suitably R.sub.9 stands for a methyl group, an ethyl group,
an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl
group, an n-octyl group or an n-dodecyl group. Suitable, R.sub.9
stands for a methyl group, an ethyl group or an n-octyl group.
In the organic silicon compounds of formula (IV), the radical
R.sub.10 represents a hydrogen atom or a C.sub.1-C.sub.6 alkyl
group. R10 stands for a methyl group or an ethyl group.
In the organic silicon compounds of formula (IV), the radical
R.sub.11 represents a C.sub.1-C.sub.6 alkyl group. R11 stands for a
methyl group or an ethyl group.
Furthermore, k stands for a whole number from 1 to 3, and m stands
for the whole number 3-k. If k stands for the number 3, then m is
equal to 0. If k stands for the number 2, then m is equal to 1. If
k stands for the number 1, then m is equal to 2.
Dyes with the best wash fastness values could be obtained if an
agent (a) were used in the process which contains at least one
organic silicon compound of the formula (IV) in which the radical k
stands for the number 3. In this case the rest m stands for the
number 0.
Organic silicon compounds of the formula (IV) which are
particularly suitable for solving the problem as contemplated
herein are.
##STR00004##
In another exemplary embodiment, a process as contemplated herein
the agent (a) contains at least one organic silicon compound of
formula (IV) selected from the group including
Methyltrimethoxysilane Methyltriethoxysilane Ethyltrimethoxysilane
Ethyltriethoxysilane Hexyltrimethoxysilane Hexyltriethoxysilane
Octyltrimethoxysilane Octyltriethoxysilane Dodecyltrimethoxysilane
and/or Dodecyltriethoxysilane.
In an explicitly suitable embodiment, a process as contemplated
herein an agent (a) is applied to the keratinous material which
contains at least one organic silicon compound of the formula (I)
which is selected from the group including
(3-aminopropyl)triethoxysilane and (3-aminopropyl)trimethoxysilane,
and additionally contains at least one organic silicone compound of
formula (IV) selected from the group including
methyltrimethoxysilane, methyltriethoxysilane,
ethyltrimethoxysilane and ethyltriethoxysilane.
The organic silicon compounds described above are reactive
compounds. In this context, it has been found to be exemplary if
the agent (a) of the present disclosure--based on the total weight
of agent (a)--contains one or more organic silicon compounds in a
total amount of from about 0.1 to about 20.0% by weight, suitably
from about 1.0 to about 15.0% by weight and particularly suitably
from about 2.0 to about 8.0% by weight.
In a further exemplary embodiment, a process as contemplated herein
the agent (a)--based on the total weight of agent (a)--contains one
or more organic silicon compounds in a total amount of from about
0.1 to about 20.0% by weight, suitably from about 1.0 to about
15.0% by weight and particularly suitably from about 2.0 to about
8.0% by weight.
To achieve particularly good dyeing results, it is particularly
advantageous to use the organic silicon compounds of the formula
(I) and/or (II) in certain quantity ranges on average (a).
Particularly suitably, the agent (a) contains--based on the total
weight of the agent (a)--one or more organic silicon compounds of
the formula (I) and/or (II) in a total amount of from about 0.1 to
about 10.0% by weight, suitably from about 0.5 to about 5.0% by
weight and particularly suitably from about 1.0 to about 3.0% by
weight.
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains--based on the total weight of the agent
(a)--one or more organic silicon compounds of the formula (I)
and/or (II) in a total amount of from about 0.1 to about 10.0% by
weight, suitably from about 0.5 to about 5.0% by weight and
particularly suitably from about 1.0 to about 3.0% by weight.
Furthermore, it has proven to be suitable if the organic silicon
compound(s) of formula (IV) is (are) also present in certain
quantity ranges in average (a). Particularly suitably the agent (a)
contains--based on the total weight of agent (a)--one or more
organic silicon compounds of the formula (IV) in a total amount of
from about 0.1 to about 20.0% by weight, suitably from about 2.0 to
about 15.0% by weight and particularly suitably from about 4.0 to
about 9.0% by weight.
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains--based on the total weight of the agent
(a)--one or more organic silicon compounds of the formula (IV) in a
total amount of from about 0.1 to about 20.0% by weight, suitably
from about 2.0 to about 15.0% by weight and particularly suitably
from about 4.0 to about 9.0% by weight.
Oligoalkylsiloxanes
As a second constituent essential to the present disclosure, the
composition (a) contains at least one oligoalkylsiloxane.
For the purposes of the present disclosure, oligoalkylsiloxanes are
understood to be oligomeric siloxanes, which may be linear or
cyclic.
Exemplary linear oligoalkylsiloxanes are compounds of the general
formula (V)
##STR00005## where z is an integer from 0 to 10. Suitably, z stands
for the numbers 0, 1, 2 or 3.
Very suitable linear oligoalkylsiloxanes are for example.
##STR00006##
Hexamethyldisiloxane has the CAS number 107-46-0 and can be
purchased commercially from Sigma-Aldrich, for example.
Octamethyltrisiloxane has the CAS number 107-51-7 and is also
commercially available from Sigma-Aldrich.
Decamethyltetrasiloxane carries the CAS number 141-62-8 and is also
commercially available from Sigma-Aldrich.
Exemplary cyclic oligoalkylsiloxanes are compounds of the general
formula (VI)
##STR00007## where y is an integer from 1 to 5. Suitably, z stands
for the numbers 1, 2 or 3.
Very suitable cyclic oligoalkylsiloxanes include.
Hexamethylcyclotrisiloxane Octamethylcyclotetrasiloxane
Decamethylcyclopentasiloxane
In a further exemplary embodiment, a method as contemplated herein
the agent (a) includes at least one linear and/or cyclic
oligoalkylsiloxane.
In a further exemplary embodiment, a method as contemplated herein
the composition (a) includes at least one oligoalkylsiloxane of the
formula (V) and/or (VI),
##STR00008## where z is an integer from 0 to 10, suitably an
integer from 0 to 3,
##STR00009## where y is an integer from 1 to 5, suitably an integer
from 1 to 3.
In a further exemplary embodiment, a method as contemplated herein
the composition (a) includes at least one oligoalkylsiloxane
selected from the group including hexamethyldisiloxane,
octamethyltrisiloxane, decamethyltetrasiloxane,
hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and/or
decamethylcyclopentasiloxane.
In contrast to the reactive organic silicon compounds, i.e., the
silanes of formulae (I), (II) and (IV), the oligoalkylsiloxanes are
composed exclusively of dialkylsilyl groups (dimethylsilyl groups)
and trialkylsilyl groups (trimethylsilyl groups), which are linked
to one another via oxygen atoms. Thus, the oligoalkylsiloxanes
themselves are not reactive compounds and do not possess
hydrolysable groups.
It was found that the agents (a), which in addition to the organic
silicon compounds (silanes) also contained oligoalkylsiloxanes, had
particularly good storage stability. Without being limited to this
theory, it is believed that the reactive organic silicic compounds
(especially the silane formulas (I), (II), and (IV)) dissolve very
well in the oligoalkylsiloxanes, with the inert character of the
oligoalkylsiloxanes preventing the silanes from reacting too
quickly and protecting the silanes from atmospheric moisture. In
this way, the silanes contained in agent (a) did not react
prematurely in an undesirable manner, and their reactivity was
preserved.
When used in the dyeing process, it was shown that a consistently
good color result could be achieved in this way, regardless of the
conditions prevailing during dyeing. Stains applied at high
humidity were as good as those applied at lower humidity.
Therefore, it was also possible to achieve a particularly high
color intensity when using agent (a) in the process as contemplated
herein, since a particularly homogeneous film was formed on the
keratin material when agent (a) was applied, which still had enough
reactive sites to bind the direct dyes of agent (b).
This effect could be achieved when the agent (a) contained the
oligoalkylsiloxane(s) in certain amount ranges. It has been found
to be suitable if the agent (a)--based on the total weight of the
agent (a)--contains one or more oligoalkylsiloxanes in a total
amount of from about 0.1 to about 25.0% by weight, suitably from
about 1.0 to about 15.0% by weight-5, more suitably from about 1.5
to about 10.0% by weight and very particularly suitably from about
2.0 to about 9.0% by weight.
In a further exemplary embodiment, a process as contemplated herein
the agent (a) contains--based on the total weight of the agent
(a)--one or more oligoalkylsiloxanes in a total amount of from
about 0.1 to about 25.0% by weight, suitably from about 1.0 to
about 15.0% by weight-5, more suitably from about 1.5 to about
10.0% by weight and very particularly suitably from about 2.0 to
about 9.0% by weight.
For optimum control of the rate of polymerization of the silanes,
it has further been found to be particularly advantageous to use
the organic silicon compounds and the oligoalkylsilxoans in
specific proportions in the medium (a).
In a further exemplary embodiment, a process as contemplated herein
the weight ratio of all organic silicon compounds of the formulae
(I), (II) and (IV) contained in the agent (a) to all
oligoalkylsiloxanes of the formulae (V) and (VI) contained in the
agent (a) is from about 5:1 to about 1:1, suitably from about 3:1
to about 1:1 and particularly suitably from about 2:1 to about
1:1.
Example: An agent (a) contains: about 2.0% by weight
3-aminopropyltriethoxysilane and about 7.0 wt. %
methyltrimethoxsilane and about 5.0 wt. % hexamethyldisiloxane The
weight ratio of all organic silicon compounds of formulae (I), (II)
and (IV) contained in the medium (a) to all oligoalkylsiloxanes of
formulae (V) and (VI) contained in the medium (a) is
(2.0+7.0)/5.0=1.8
Particularly resistant strains could be obtained when using an
alkaline adjusted agent (a). Suitably, agent (a) contains water and
has a pH of from about 7.0 to about 11.5, suitably from about 7.5
to about 11.0, and more suitably from about 8.0 to about 10.5.
In another very suitable embodiment, a process as contemplated
herein the agent (a) has a pH of from about 7.0 to about 11.5,
suitably from about 7.5 to about 11.0 and particularly suitably
from about 8.0 to about 10.5.
Agent (b)
The agent (b) is exemplified by its content of at least one pigment
and/or a direct dye. The agent (b) may also be called colorant
(b).
Pigments within the meaning of the present disclosure are coloring
compounds which have a solubility in water at about 25.degree. C.
of less than about 0.5 g/L, suitably less than about 0.1 g/L, even
more suitably less than about 0.05 g/L. Water solubility can be
determined, for example, by the method described below: about 0.5 g
of the pigment are weighed in a beaker. A stir-fish is added. Then
one liter of distilled water is added. This mixture is heated to
about 25.degree. C. for one hour while stirring on a magnetic
stirrer. If undissolved components of the pigment are still visible
in the mixture after this period, the solubility of the pigment is
below about 0.5 g/L. If the pigment-water mixture cannot be
assessed visually due to the high intensity of the possibly finely
dispersed pigment, the mixture is filtered. If a proportion of
undissolved pigments remains on the filter paper, the solubility of
the pigment is below about 0.5 g/L.
Suitable color pigments can be of inorganic and/or organic
origin.
In a exemplary embodiment, an agent (b) of the present disclosure
contains at least one colorant compound from the group of inorganic
and/or organic pigments.
Exemplary color pigments are selected from synthetic or natural
inorganic pigments. Inorganic color pigments of natural origin can
be produced, for example, from chalk, ochre, umber, green earth,
burnt Terra di Siena or graphite. Furthermore, black pigments such
as iron oxide black, colored pigments such as ultramarine or iron
oxide red as well as fluorescent or phosphorescent pigments can be
used as inorganic color pigments.
Particularly suitable are colored metal oxides, hydroxides and
oxide hydrates, mixed-phase pigments, sulfur-containing silicates,
silicates, metal sulphides, complex metal cyanides, metal
sulphates, chromates and/or molybdates. Exemplary color pigments
are black iron oxide (CI 77499), yellow iron oxide (CI 77492), red
and brown iron oxide (CI 77491), manganese violet (CI 77742),
ultramarine (sodium aluminum sulfo silicates, CI 77007, pigment
blue 29), chromium oxide hydrate (CI77289), iron blue (ferric
ferrocyanides, CI77510) and/or carmine (cochineal).
As contemplated herein, colored pearlescent pigments are also
suitable color pigments. These are usually mica- and/or mica-based
and can be coated with one or more metal oxides. Mica belongs to
the layer silicates. The most important representatives of these
silicates are muscovite, phlogopite, paragonite, biotite,
lepidolite and margarite. To produce the pearlescent pigments in
combination with metal oxides, the mica, mainly muscovite or
phlogopite, is coated with a metal oxide.
As an alternative to natural mica, synthetic mica coated with one
or more metal oxides can also be used as pearlescent pigment.
Especially exemplary pearlescent pigments are based on natural or
synthetic mica (mica) and are coated with one or more of the metal
oxides mentioned above. The color of the respective pigments can be
varied by varying the layer thickness of the metal oxide(s).
In a further exemplary embodiment, a process as contemplated herein
the agent (b) contains at least one colorant compound from the
group of pigments selected from the group of colored metal oxides,
metal hydroxides, metal oxide hydrates, silicates, metal sulfides,
complex metal cyanides, metal sulfates, bronze pigments and/or from
colored pigments based on mica or mica which are coated with at
least one metal oxide and/or one metal oxychloride.
In a further exemplary embodiment, an agent as contemplated herein
contains (b) at least one colorant compound from the group of
pigments selected from pigments based on mica or micaceous iron
oxide, which is combined with one or more metal oxides from the
group of titanium dioxide (CI 77891), are coated with black iron
oxide (CI 77499), yellow iron oxide (CI 77492), red and/or brown
iron oxide (CI 77491, CI 77499), manganese violet (CI 77742),
ultramarine (sodium aluminum sulfo silicates, CI 77007, pigment
blue 29), chromium oxide hydrate (CI 77289), chromium oxide (CI
77288) and/or iron blue (ferric ferrocyanides, CI 77510).
Examples of particularly suitable color pigments are commercially
available under the trade names Rona.RTM., Colorona.RTM.,
Xirona.RTM., Dichrona.RTM. and Timiron.RTM. from Merck,
Ariabel.RTM. and Unipure.RTM. from Sensient, Prestige.RTM. from
Eckart Cosmetic Colors and Sunshine.RTM. from Sunstar.
Suitable color pigments with the trade name Colorona.RTM. are, for
example:
Colorona Copper, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Passion Orange, Merck, Mica, CI 77491 (Iron Oxides),
Alumina
Colorona Patina Silver, Merck, MICA, CI 77499 (IRON OXIDES), CI
77891 (TITANIUM DIOXIDE)
Colorona RY, Merck, CI 77891 (TITANIUM DIOXIDE), MICA, CI 75470
(CARMINE)
Colorona Oriental Beige, Merck, MICA, CI 77891 (TITANIUM DIOXIDE),
CI 77491 (IRON OXIDES)
Colorona Dark Blue, Merck, MICA, TITANIUM DIOXIDE, FERRIC
FERROCYANIDE
Colorona Chameleon, Merck, CI 77491 (IRON OXIDES), MICA
Colorona Aborigine Amber, Merck, MICA, CI 77499 (IRON OXIDES), CI
77891 (TITANIUM DIOXIDE)
Colorona Blackstar Blue, Merck, CI 77499 (IRON OXIDES), MICA
Colorona Patagonian Purple, Merck, MICA, CI 77491 (IRON OXIDES), CI
77891 (TITANIUM DIOXIDE), CI 77510 (FERRIC FERROCYANIDE)
Colorona Red Brown, Merck, MICA, CI 77491 (IRON OXIDES), CI 77891
(TITANIUM DIOXIDE)
Colorona Russet, Merck, CI 77491 (TITANIUM DIOXIDE), MICA, CI 77891
(IRON OXIDES)
Colorona Imperial Red, Merck, MICA, TITANIUM DIOXIDE (CI 77891),
D&C RED NO. 30 (CI 73360)
Colorona Majestic Green, Merck, CI 77891 (TITANIUM DIOXIDE), MICA,
CI 77288 (CHROMIUM OXIDE GREENS)
Colorona Light Blue, Merck, MICA, TITANIUM DIOXIDE (CI 77891),
FERRIC FERROCYANIDE (CI 77510)
Colorona Red Gold, Merck, MICA, CI 77891 (TITANIUM DIOXIDE), CI
77491 (IRON OXIDES)
Colorona Gold Plus MP 25, Merck, MICA, TITANIUM DIOXIDE (CI 77891),
IRON OXIDES (CI 77491)
Colorona Carmine Red, Merck, MICA, TITANIUM DIOXIDE, CARMINE
Colorona Blackstar Green, Merck, MICA, CI 77499 (IRON OXIDES)
Colorona Bordeaux, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Bronze, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Bronze Fine, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Fine Gold MP 20, Merck, MICA, CI 77891 (TITANIUM DIOXIDE),
CI 77491 (IRON OXIDES)
Colorona Sienna Fine, Merck, CI 77491 (IRON OXIDES), MICA
Colorona Sienna, Merck, MICA, CI 77491 (IRON OXIDES)
Colorona Precious Gold, Merck, Mica, CI 77891 (Titanium dioxide),
Silica, CI 77491 (Iron oxides), Tin oxide
Colorona Sun Gold Sparkle MP 29, Merck, MICA, TITANIUM DIOXIDE,
IRON OXIDES, MICA, CI 77891, CI 77491 (EU)
Colorona Mica Black, Merck, CI 77499 (Iron oxides), Mica, CI 77891
(Titanium dioxide)
Colorona Bright Gold, Merck, Mica, CI 77891 (Titanium dioxide), CI
77491 (Iron oxides)
Colorona Blackstar Gold, Merck, MICA, CI 77499 (IRON OXIDES)
Other suitable color pigments with the trade name Xirona.RTM. are
for example:
Xirona Golden Sky, Merck, Silica, CI 77891 (Titanium Dioxide), Tin
Oxide
Xirona Caribbean Blue, Merck, Mica, CI 77891 (Titanium Dioxide),
Silica, Tin Oxide
Xirona Kiwi Rose, Merck, Silica, CI 77891 (Titanium Dioxide), Tin
Oxide
Xirona Magic Mauve, Merck, Silica, CI 77891 (Titanium Dioxide), Tin
Oxide.
In addition, suitable color pigments with the trade name
Unipure.RTM. are for example:
Unipure Red LC 381 EM, Sensient CI 77491 (Iron Oxides), Silica
Unipure Black LC 989 EM, Sensient, CI 77499 (Iron Oxides),
Silica
Unipure Yellow LC 182 EM, Sensient, CI 77492 (Iron Oxides),
Silica
In a further embodiment, the means as contemplated herein may also
contain (b) one or more coloring compounds from the group of
organic pigments.
The organic pigments as contemplated herein are correspondingly
insoluble, organic dyes or color lacquers, which may be selected,
for example, from the group of nitroso, nitro-azo, xanthene,
anthraquinone, isoindolinone, isoindolinone, quinacridone,
perinone, perylene, diketo-pyrrolopyorrole, indigo, thioindido,
dioxazine and/or triarylmethane compounds.
Examples of particularly suitable organic pigments are carmine,
quinacridone, phthalocyanine, sorghum, blue pigments with the Color
Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI
74160, yellow pigments with the Color Index numbers CI 11680, CI
11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000,
CI 47005, green pigments with the Color Index numbers CI 61565, CI
61570, CI 74260, orange pigments with the Color Index numbers CI
11725, CI 15510, CI 45370, CI 71105, red pigments with the Color
Index numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI
14700, CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850,
CI 15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI
58000, CI 73360, CI 73915 and/or CI 75470.
In a further suitable embodiment, a process as contemplated herein
the agent (b) contains at least one colorant compound from the
group of organic pigments selected from the group of carmine,
quinacridone, phthalocyanine, sorghum, blue pigments with the Color
Index numbers CI 42090, CI 69800, CI 69825, CI 73000, CI 74100, CI
74160, yellow pigments with the Color Index numbers CI 11680, CI
11710, CI 15985, CI 19140, CI 20040, CI 21100, CI 21108, CI 47000,
CI 47005, green pigments with Color Index numbers CI 61565, CI
61570, CI 74260, orange pigments with Color Index numbers CI 11725,
CI 15510, CI 45370, CI 71105, red pigments with the Color Index
numbers CI 12085, CI 12120, CI 12370, CI 12420, CI 12490, CI 14700,
CI 15525, CI 15580, CI 15620, CI 15630, CI 15800, CI 15850, CI
15865, CI 15880, CI 17200, CI 26100, CI 45380, CI 45410, CI 58000,
CI 73360, CI 73915 and/or CI 75470.
The organic pigment can also be a color paint. As contemplated
herein, the term color lacquer means particles including a layer of
absorbed dyes, the unit of particle and dye being insoluble under
the above-mentioned conditions. The particles can, for example, be
inorganic substrates, which can be aluminum, silica, calcium
borosilate, calcium aluminum borosilicate or even aluminum.
For example, alizarin color varnish can be used.
Due to their excellent light and temperature resistance, the use of
the pigments in agent (b) of the process as contemplated herein is
suitable. It is also exemplary if the pigments used have a certain
particle size. As contemplated herein, it is therefore advantageous
if the at least one pigment has an average particle size D.sub.50
of from about 1.0 to about 50 .mu.m, suitably from about 5.0 to
about 45 .mu.m, suitably from about 10 to about 40 .mu.m, from
about 14 to about 30 .mu.m. The mean particle size D.sub.50, for
example, can be determined using dynamic light scattering
(DLS).
The pigment or pigments may be used in an amount of from about
0.001 to about 20% by weight, of from about 0.05 to about 5% by
weight, each based on the total weight of agent (b).
As colorant compounds, the agents (b) used in the process as
contemplated herein may also contain one or more direct dyes.
Direct-acting dyes are dyes that draw directly onto the hair and do
not require an oxidative process to form the color. Direct dyes are
usually nitro phenylene diamines, nitroaminophenols, azo dyes,
anthraquinones, triarylmethane dyes or indophenols.
The direct dyes within the meaning of the present disclosure have a
solubility in water (760 mmHg) at about 25.degree. C. of more than
about 0.5 g/L and are therefore not to be regarded as pigments.
Suitably, the direct dyes within the meaning of the present
disclosure have a solubility in water (760 mmHg) at about
25.degree. C. of more than about 1.0 g/L.
Direct dyes can be divided into anionic, cationic, and non-ionic
direct dyes.
In a further exemplary embodiment, an agent as contemplated herein
contains as coloring compound (b) at least one anionic, cationic
and/or non-ionic direct dye.
In a further exemplary embodiment, an agent as contemplated herein
contains (b) at least one anionic, cationic and/or non-ionic direct
dye.
Suitable cationic direct dyes include Basic Blue 7, Basic Blue 26,
Basic Violet 2, and Basic Violet 14, Basic Yellow 57, Basic Red 76,
Basic Blue 16, Basic Blue 347 (Cationic Blue 347/Dystar), HC Blue
No. 16, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Yellow
57, Basic Yellow 87, Basic Orange 31, Basic Red 51 Basic Red 76
As non-ionic direct dyes, non-ionic nitro and quinone dyes and
neutral azo dyes can be used. Suitable non-ionic direct dyes are
those listed under the international designations or Trade names HC
Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12, HC
Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 10, HC Red
11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12,
Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4,
Disperse Black 9 known compounds, as well as
1,4-diamino-2-nitrobenzene, 2-amino-4-nitrophenol,
1,4-bis-(2-hydroxyethyl)-amino-2-nitrobenzene,
3-nitro-4-(2-hydroxyethyl)-aminophenol
2-(2-hydroxyethyl)amino-4,6-dinitrophenol,
4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,
1-amino-4-(2-hydroxyethyl)-amino-5-chloro-2-nitrobenzene,
4-amino-3-nitrophenol, 1-(2'-ureidoethyl)amino-4-nitrobenzene,
2-[(4-amino-2-nitrophenyl)amino]benzoic acid,
6-nitro-1,2,3,4-tetrahydroquinoxaline,
2-hydroxy-1,4-naphthoquinone, picramic acid and its salts,
2-amino-6-chloro-4-nitrophenol, 4-ethylamino-3-nitrobenzoic acid
and 2-chloro-6-ethylamino-4-nitrophenol.
In a further exemplary embodiment, a process as contemplated herein
the agent (b) includes at least one direct dye selected from the
group including anionic, cationic, and nonionic direct dyes.
In the course of the work leading to the present disclosure, it has
been found that dyeing's of particularly high color intensity can
be produced with agents (b) containing at least one anionic direct
dye.
In an explicitly quite suitable embodiment, an agent (b) used in
the process as contemplated herein contains at least one anionic
direct dye.
Anionic direct dyes are also called acid dyes. Acid dyes are direct
dyes that have at least one carboxylic acid group (--COOH) and/or
one sulphonic acid group (--SO.sub.3H). Depending on the pH value,
the protonated forms (--COOH, --SO.sub.3H) of the carboxylic acid
or sulphonic acid groups are in equilibrium with their deprotonated
forms (--COO.sup.-, --SO.sub.3.sup.- present). The proportion of
protonated forms increases with decreasing pH value. If direct dyes
are used in the form of their salts, the carboxylic acid groups or
sulphonic acid groups are present in deprotonated form and are
neutralized with corresponding stoichiometric equivalents of
cations to maintain electro neutrality. Inventive acid dyes can
also be used in the form of their sodium salts and/or their
potassium salts.
The acid dyes within the meaning of the present disclosure have a
solubility in water (760 mmHg) at about 25.degree. C. of more than
about 0.5 g/L and are therefore not to be regarded as pigments.
Suitably the acid dyes within the meaning of the present disclosure
have a solubility in water (760 mmHg) at about 25.degree. C. of
more than about 1.0 g/L.
The alkaline earth salts (such as calcium salts and magnesium
salts) or aluminum salts of acid dyes often have a lower solubility
than the corresponding alkali salts. If the solubility of these
salts is below about 0.5 g/L (25.degree. C., 760 mmHg), they do not
fall under the definition of a direct dye.
An essential characteristic of acid dyes is their ability to form
anionic charges, whereby the carboxylic acid or sulphonic acid
groups responsible for this are usually linked to different
chromophoric systems. Suitable chromophoric systems can be found,
for example, in the structures of nitrophenylenediamines,
nitroaminophenols, azo dyes, anthraquinone dyes, triarylmethane
dyes, xanthene dyes, rhodamine dyes, oxazine dyes and/or indophenol
dyes.
In one embodiment of the process, the use of an agent (b) which
contains at least one anionic direct dye selected from the group
including nitrophenylenediamines, nitroaminophenols, azo dyes,
anthraquinone dyes, triarylmethane dyes, xanthene dyes, rhodamine
dyes, oxazine dyes and/or indophenol dyes is thus exemplary, the
rhodamine dyes, the oxazine dyes and/or the indophenol dyes, the
dyes from the abovementioned group each having at least one
carboxylic acid group (--COOH), a sodium carboxylate group
(--COONa), a potassium carboxylate group (--COOK), a sulfonic acid
group (--SO.sub.3H), a sodium sulfonate group (--SO.sub.3Na) and/or
a potassium sulfonate group (--SO.sub.3K).
For example, one or more compounds from the following group can be
selected as particularly well suited acid dyes: Acid Yellow 1
(D&C Yellow 7, Citronin A, Ext. D&C Yellow No. 7, Japan
Yellow 403, CI 10316, COLIPA no B001), Acid Yellow 3 (COLIPA
n.degree.: C 54, D&C Yellow No 10, Quinoline Yellow, E104, Food
Yellow 13), Acid Yellow 9 (CI 13015), Acid Yellow 17 (CI 18965),
Acid Yellow 23 (COLIPA no C. 29, Covacap Jaune W 1100 (LCW),
Sicovit Tartrazine 85 E 102 (BASF), Tartrazine, Food Yellow 4,
Japan Yellow 4, FD&C Yellow No. 5), Acid Yellow 36 (CI 13065),
Acid Yellow 121 (CI 18690), Acid Orange 6 (CI 14270), Acid Orange 7
(2-Naphthol orange, Orange II, CI 15510, D&C Orange 4, COLIPA
no C015), Acid Orange 10 (C.I. 16230; Orange G sodium salt), Acid
Orange 11 (CI 45370), Acid Orange 15 (CI 50120), Acid Orange 20 (CI
14600), Acid Orange 24 (BROWN 1; CI 20170; KATSU201; no sodium
salt; Brown No. 201; RESORCIN BROWN; ACID ORANGE 24; Japan Brown
201; D & C Brown No. 1), Acid Red 14 (C.I. 14720), Acid Red 18
(E124, Red 18; CI 16255), Acid Red 27 (E 123, CI 16185, C-Rot 46,
Echtrot D, FD&C Red Nr. 2, Food Red 9, Naphtholrot S), Acid Red
33 (Red 33, Fuchsia Red, D&C Red 33, CI 17200), Acid Red 35 (CI
C.I. 18065), Acid Red 51 (CI 45430, Pyrosin B, Tetraiodfluorescein,
Eosin J, Iodeosin), Acid Red 52 (CI 45100, Food Red 106, Solar
Rhodamine B, Acid Rhodamine B, Red no 106 Pontacyl Brilliant Pink),
Acid Red 73 (CI 27290), Acid Red 87 (Eosin, CI 45380), Acid Red 92
(COLIPA no C53, CI 45410), Acid Red 95 (CI 45425, Erythtosine,
Simacid Erythrosine Y), Acid Red 184 (CI 15685), Acid Red 195, Acid
Violet 43 (Jarocol Violet 43, Ext. D&C Violet no 2, C.I. 60730,
COLIPA no C063), Acid Violet 49 (CI 42640), Acid Violet 50 (CI
50325), Acid Blue 1 (Patent Blue, CI 42045), Acid Blue 3 (Patent
Blue V, CI 42051), Acid Blue 7 (CI 42080), Acid Blue 104 (CI
42735), Acid Blue 9 (E 133, Patent blue AE, Amidoblau AE,
Erioglaucin A, CI 42090, C.I. Food Blue 2), Acid Blue 62 (CI
62045), Acid Blue 74 (E 132, CI 73015), Acid Blue 80 (CI 61585),
Acid Green 3 (CI 42085, Foodgreen1), Acid Green 5 (CI 42095), Acid
Green 9 (C.I. 42100), Acid Green 22 (C.I. 42170), Acid Green 25 (CI
61570, Japan Green 201, D&C Green No. 5), Acid Green 50
(Brilliant Acid Green BS, C.I. 44090, Acid Brilliant Green BS, E
142), Acid Black 1 (Black no 401, Naphthalene Black 10B, Amido
Black 10B, CI 20 470, COLIPA no B15), Acid Black 52 (CI 15711),
Food Yellow 8 (CI 14270), Food Blue 5, D&C Yellow 8, D&C
Green 5, D&C Orange 10, D&C Orange 11, D&C Red 21,
D&C Red 27, D&C Red 33, D&C Violet 2 and/or D&C
Brown 1.
The water solubility of direct dyes can be determined, for example,
in the following way. about 0.1 g of the anionic dye is added to a
beaker. A stir-fish is added. Then add about 100 ml of water. This
mixture is heated to about 25.degree. C. on a magnetic stirrer
while stirring. It is stirred for about 60 minutes. The aqueous
mixture is then visually assessed. If there are still undissolved
residues, the amount of water is increased--for example in steps of
10 ml. Water is added until the amount of dye used is completely
dissolved. If the dye-water mixture cannot be assessed visually due
to the high intensity of the dye, the mixture is filtered. If a
proportion of undissolved dyes remains on the filter paper, the
solubility test is repeated with a higher quantity of water. If
about 0.1 g of the anionic direct dye dissolves in about 100 ml
water at 25.degree. C., the solubility of the dye is about 1.0
g/L.
Acid Yellow 1 is called 8-hydroxy-5,7-dinitro-2-naphthalenesulfonic
acid disodium salt and has a solubility in water of at least about
40 g/L (25.degree. C.).
Acid Yellow 3 is a mixture of the sodium salts of mono- and
sisulfonic acids of 2-(2-quinolyl)-1H-indene-1,3(2H)-dione and has
a water solubility of about 20 g/L (25.degree. C.).
Acid Yellow 9 is the disodium salt of
8-hydroxy-5,7-dinitro-2-naphthalenesulfonic acid, its solubility in
water is above about 40 g/L (25.degree. C.).
Acid Yellow 23 is the trisodium salt of
4,5-dihydro-5-oxo-1-(4-sulfophenyl)-4-((4-sulfophenyl)azo)-1H-pyrazole-3--
carboxylic acid and is highly soluble in water at about 25.degree.
C.
Acid Orange 7 is the sodium salt of
4-[(2-hydroxy-1-naphthyl)azo]benzene sulphonate. Its water
solubility is more than about 7 g/L (25.degree. C.).
Acid Red 18 is the trinatirum salt of
7-hydroxy-8-[(E)-(4-sulfonato-1-naphthyl)-diazenyl)]-1,3-naphthalene
disulfonate and has a very high-water solubility of more than about
20% by weight.
Acid Red 33 is the diantrium salt of
5-amino-4-hydroxy-3-(phenylazo)-naphthalene-2,7-disulphonate, its
solubility in water is about 2.5 g/L (25.degree. C.).
Acid Red 92 is the disodium salt of
3,4,5,6-tetrachloro-2-(1,4,5,8-tetrabromo-6-hydroxy-3-oxoxanthen-9-yl)ben-
zoic acid, whose solubility in water is indicated as greater than
about 10 g/L (25.degree. C.).
Acid Blue 9 is the disodium salt of
2-({4-[N-ethyl(3-sulfonatobenzyl]amino]phenyl}{4-[(N-ethyl(3-sulfonatoben-
zyl)imino]-2,5-cyclohexadien-1-ylidene}methyl)-benzenesulfonate and
has a solubility in water of more than about 20% by weight
(25.degree. C.).
A very suitable process as contemplated herein the agent (b)
includes at least one anionic direct dye selected from the group
including Acid Yellow 1, Acid Yellow 3, Acid Yellow 9, Acid Yellow
17, Acid Yellow 23, Acid Yellow 36, Acid Yellow 121, Acid Orange 6,
Acid Orange 7, Acid Orange 10, Acid Orange 11, Acid Orange 15, Acid
Orange 20, Acid Orange 24, Acid Red 14, Acid Red, Acid Red 27, Acid
Red 33, Acid Red 35, Acid Red 51, Acid Red 52, Acid Red 73, Acid
Red 87, Acid Red 92, Acid Red 95, Acid Red 184, Acid Red 195, Acid
Violet 43, Acid Violet 49, Acid Violet 50, Acid Blue 1, Acid Blue
3, Acid Blue 7, Acid Blue 104, Acid Blue 9, Acid Blue 62, Acid Blue
74, Acid Blue 80, Acid Green 3, Acid Green 5, Acid Green 9, Acid
Green 22, Acid Green 25, Acid Green 50, Acid Black 1, Acid Black
52, Food Yellow 8, Food Blue 5, D&C Yellow 8, D&C Green 5,
D&C Orange 10, D&C Orange 11, D&C Red 21, D&C Red
27, D&C Red 33, D&C Violet 2 and/or D&C Brown 1.
The direct dye(s), in the anionic direct dyes, can be used in
different amounts in the agent (b) depending on the desired color
intensity. Particularly good results were obtained when the agent
(b)--based on the total weight of the agent (b)--contains one or
more direct dyes in a total amount of from about 0.01 to about
10.0% by weight, suitably from about 0.1 to about 8.0% by weight,
more suitably from about 0.2 to about 6.0% by weight and most
suitably from about 0.5 to about 4.5% by weight.
In a further exemplary embodiment, an agent (b) contains--based on
the total weight of the agent (b)--one or more direct dyes in a
total amount of from about 0.01 to about 10.0% by weight, suitably
from about 0.1 to about 8.0% by weight, more suitably from about
0.2 to about 6.0% by weight and most suitably from about 0.5 to
about 4.5% by weight.
In a further exemplary embodiment, an agent as contemplated herein
contains--based on the total weight of the agent (b)--one or more
anionic direct dyes (b) in a total amount of from about 0.01 to
about 10.0% by weight, suitably from about 0.1 to about 8.0% by
weight, more suitably from about 0.2 to about 6.0% by weight and
very particularly suitably from about 0.5 to about 4.5% by
weight.
Other Ingredients in Products (a) and (b)
The agents (a) and (b) described above may also contain one or more
optional ingredients.
The products may also contain one or more surfactants. The term
surfactants refer to surface-active substances. A distinction is
made between anionic surfactants including a hydrophobic residue
and a negatively charged hydrophilic head group, amphoteric
surfactants, which carry both a negative and a compensating
positive charge, cationic surfactants, which in addition to a
hydrophobic residue have a positively charged hydrophilic group,
and non-ionic surfactants, which have no charges but strong dipole
moments and are strongly hydrated in aqueous solution.
Zwitterionic surfactants are those surface-active compounds which
carry at least one quaternary ammonium group and at least one
--COO.sup.(-)-- or --SO.sub.3.sup.(-) group in the molecule.
Particularly suitable zwitterionic surfactants are the so-called
betaines such as the N-alkyl-N,N-dimethylammonium-glycinate, for
example the cocoalkyl-dimethylammoniumglycinate,
N-acylaminopropyl-N,N-dimethylammoniumglycinate, for example,
cocoacylaminopropyl dimethyl ammonium glycinate, and
2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines each having 8
to 18 C atoms in the alkyl or acyl group, and cocoacylaminoethyl
hydroxyethyl carboxymethyl glycinate. A exemplary zwitterionic
surfactant is the fatty acid amide derivative known under the INCI
name cocamidopropyl betaine.
Ampholytic surfactants are surface-active compounds which, apart
from a C.sub.8-C.sub.24 alkyl or acyl group, contain at least one
free amino group and at least one --COOH-- or --SO.sub.3H group in
the molecule and can form internal salts. Examples of suitable
ampholytic surfactants are N-alkylglycines, N-alkylpropionic acids,
N-alkylaminobutyric acids, N-alkyliminodipropionic acids,
N-hydroxyethyl-N-alkylamidopropylglycines, N-alkyltaurines,
N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic
acids each with about 8 to 24 C atoms in the alkyl group. Typical
examples of amphoteric or zwitterionic surfactants are
alkylbetaines, alkylamidobetaines, amino propionates,
aminoglycinate, imidazoliniumbetaines and sulfobetaines.
Suitable ampholytic surfactants are N-cocoalkylaminopropionate,
cocoacylaminoethylaminopropionate and C.sub.12-C.sub.18
acylsarcosine.
The products may also additionally contain at least one non-ionic
surfactant. Suitable non-ionic surfactants are alkyl polyglycosides
as well as alkylene oxide addition products to fatty alcohols and
fatty acids with 2 to 30 mol ethylene oxide per mol fatty alcohol
or fatty acid. Preparations with good properties are also obtained
if they contain as non-ionic surfactants fatty acid esters of
ethoxylated glycerol reacted with at least 2 mol ethylene oxide.
The non-ionic surfactants are used in a total quantity of from
about 0.1 to about 45% by weight, suitably from about 1 to about
30% by weight and very suitably from about 1 to about 15% by
weight--based on the total weight of the respective agent.
In addition, the products may also contain at least one cationic
surfactant. Cationic surfactants are surfactants, i.e.,
surface-active compounds, each with one or more positive charges.
Cationic surfactants contain only positive charges. Usually, these
surfactants are composed of a hydrophobic part and a hydrophilic
head group, the hydrophobic part usually including a hydrocarbon
backbone (e.g., including one or two linear or branched alkyl
chains) and the positive charge(s) being in the hydrophilic head
group. Examples of cationic surfactants are quaternary ammonium
compounds which, as hydrophobic radicals, may carry one or two
alkyl chains with a chain length of 8 to 28 C atoms, quaternary
phosphonium salts substituted with one or more alkyl chains with a
chain length of 8 to 28 C atoms or tertiary sulfonium salts.
Furthermore, the cationic charge can also be part of a heterocyclic
ring (e.g., an imidazolium ring or a pyridinium ring) in the form
of an onium structure. In addition to the functional unit carrying
the cationic charge, the cationic surfactant may also contain other
uncharged functional groups, as is the case for example with
esterquats. The cationic surfactants are used in a total quantity
of from about 0.1 to about 45 wt. %, suitably from about 1 to about
30 wt. % and most suitably from about 1 to about 15 wt. %--based on
the total weight of the respective agent.
Furthermore, the means as contemplated herein may also contain at
least one anionic surfactant. Anionic surfactants are
surface-active agents with exclusively anionic charges (neutralized
by a corresponding counter cation). Examples of anionic surfactants
are fatty acids, alkyl sulphates, alkyl ether sulphates and ether
carboxylic acids with 12 to 20 C atoms in the alkyl group and up to
16 glycol ether groups in the molecule.
The anionic surfactants are used in a total quantity of from about
0.1 to about 45 wt. %, suitably from about 1 to about 30 wt. % and
most suitably from about 1 to about 15 wt. % --based on the total
weight of the respective agent.
To adjust the desired pH, agents (a), (b) and (c) may also contain
at least one alkalizing agent and/or acidifying agent. The pH
values for the purposes of the present disclosure are pH values
measured at a temperature of about 22.degree. C.
As alkalizing agents, agents (a), (b) and (c) may contain for
example ammonia, alkanolamines and/or basic amino acids.
The alkanolamines which can be used in the composition of the
present disclosure are suitably selected from primary amines having
a C.sub.2-C.sub.6 alkyl base which carries at least one hydroxyl
group. Exemplary alkanolamines are selected from the group formed
by 2-aminoethan-1-ol (monoethanolamine), 3-aminopropan-1-ol,
4-aminobutan-1-ol, 5-aminopentan-1-ol, 1-aminopropan-2-ol,
1-aminobutan-2-ol, 1-aminopentan-2-ol, 1-aminopentan-3-ol,
1-aminopentan-4-ol, 3-amino-2-methylpropan-1-ol,
1-amino-2-methylpropan-2-ol, 3-aminopropan-1,2-diol,
2-amino-2-methylpropan-1,3-diol.
Alkanolamines suitable as contemplated herein are selected from
2-aminoethan-1-ol and/or 2-amino-2-methylpropan-1-ol. A suitable
embodiment the agent as contemplated herein contains an
alkanolamine selected from 2-aminoethan-1-ol and/or
2-amino-2-methylpropan-1-ol as alkalizing agent.
A suitable embodiment the agent as contemplated herein contains an
alkanolamine selected from 2-aminoethan-1-ol and/or
2-amino-2-methylpropan-1-ol as alkalizing agent. For the purposes
of the present disclosure, an amino acid is an organic compound
which in its structure contains at least one protonatable amino
group and at least one --COOH or one --SO.sub.3H group. Exemplary
amino acids are aminocarboxylic acids, especially
.alpha.-(alpha)-aminocarboxylic acids and .omega.-aminocarboxylic
acids, whereby .alpha.-aminocarboxylic acids are suitable.
As contemplated herein, basic amino acids are those amino acids
which have an isoelectric point pI of greater than about 7.0.
Basic .alpha.-aminocarboxylic acids contain at least one asymmetric
carbon atom. In the context of the present disclosure, both
possible enantiomers can be used equally as specific compounds or
their mixtures, especially as racemates. However, it is
particularly advantageous to use the naturally exemplary isomeric
form, usually in L-configuration.
The basic amino acids are suitably selected from the group formed
by arginine, lysine, ornithine, and histidine, especially suitably
arginine and lysine. In another suitable embodiment, an agent as
contemplated herein the alkalizing agent is a basic amino acid from
the group arginine, lysine, ornithine and/or histidine.
In addition, the product may contain other alkalizing agents,
especially inorganic alkalizing agents. Inorganic alkalizing agents
usable as contemplated herein are suitably selected from the group
formed by sodium hydroxide, potassium hydroxide, calcium hydroxide,
barium hydroxide, sodium phosphate, potassium phosphate, sodium
silicate, sodium metasilicate, potassium silicate, sodium carbonate
and potassium carbonate.
Suitable alkalizing agents are ammonia, 2-aminoethan-1-ol
(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,
5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,
1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,
3-amino-2-methylpropan-1-ol, 1-Amino-2-methylpropan-2-ol,
3-aminopropan-1,2-diol, 2-amino-2-methylpropan-1,3-diol, arginine,
lysine, ornithine, histidine, sodium hydroxide, potassium
hydroxide, calcium hydroxide, barium hydroxide, sodium phosphate,
potassium phosphate, sodium silicate, sodium metasilicate,
potassium silicate, sodium carbonate and potassium carbonate.
Acidifiers commonly used by experts are, for example, indulgence
acids such as citric acid, acetic acid, malic acid, or tartaric
acid, as well as diluted mineral acids such as hydrochloric acid,
sulfuric acid, or phosphoric acid.
They may also contain other active substances, auxiliaries and
additives, such as solvents, fatty components such as
C.sub.8-C.sub.30 fatty alcohols, C.sub.8-C.sub.30 fatty acid
triglycerides, C.sub.5-C.sub.30 fatty acid monoglycerides,
C.sub.8-C.sub.30 fatty acid diglycerides and/or hydrocarbons;
polymers, structural agents such as glucose, maleic acid and lactic
acid; hair conditioning compounds such as phospholipids, for
example lecithin and cephalins; perfume oils, dimethylisosorbide
and cyclodextrins; fiber structure-improving active substances, in
particular mono-, di- and oligosaccharides such as glucose,
galactose, fructose, fructose and lactose; dyes for coloring the
composition; anti-dandruff active substances such as Piroctone
Olamine, Zinc Omadine and Climbazol; amino acids and oligopeptides;
protein hydrolysates on animal and/or vegetable basis, as well as
in the form of their fatty acid condensation products or optionally
anionic or cationically modified derivatives; vegetable oils;
sunscreens and UV-blockers; active ingredients such as panthenol,
pantothenic acid, pantolactone, allantoin, pyrrolidinonecarboxylic
acids and their salts, and bisabolol; polyphenols, in particular
hydroxycinnamic acids, 6,7-dihydroxycumarine, hydroxybenzoic acids,
catechine, tannine, leukoanthocyanidine, anthocyanidine, flavanone,
flavone and flavonols; ceramides or pseudoceramides; vitamins,
provitamins and vitamin precursors; plant extracts; fats and waxes
such as fatty alcohols, beeswax, montan wax and paraffins; swelling
and penetrating substances such as glycerol, propylene glycol
monoethyl ether, carbonates, hydrogen carbonates, guanidines, ureas
and primary, secondary and tertiary phosphates; opacifiers such as
latex, styrene/PVP and styrene/acrylamide copolymers; pearlescent
agents such as ethylene glycol mono- and distearate and PEG-3
distearate; and blowing agents such as propane-butane mixtures,
N.sub.2O, dimethyl ether, CO.sub.2 and air.
Very particularly suitably, the composition (b) additionally
includes at least one anionic polymer selected from the group
including the copolymers of acrylic acid, the copolymers of
methacrylic acid, the homopolymers or copolymers of acrylic acid
esters, the homopolymers or copolymers of methacrylic acid esters,
the homopolymers or copolymers of acrylic acid amides, homopolymers
or copolymers of methacrylic acid amides, copolymers of
vinylpyrrolidone, copolymers of vinyl alcohol, copolymers of vinyl
acetate, homopolymers or copolymers of ethylene, homopolymers or
copolymers of propylene, homopolymers or copolymers of styrene,
polyurethanes, polyesters and/or polyamides.
The selection of these other substances will be made by the
specialist according to the desired properties of the agents.
Regarding other optional components and the quantities of these
components used, explicit reference is made to the relevant manuals
known to the specialist. The additional active ingredients and
auxiliary substances are suitably used in the preparations as
contemplated herein in quantities of from about 0.0001 to about 25
wt. % each, from about 0.0005 to about 15 wt. %, based on the total
weight of the respective agent.
Process for Dyeing Keratin Materials
In the procedure as contemplated herein, agents (a) and (b) are
applied to the keratinous materials, to human hair. Thus, agents
(a) and (b) are the ready-to-use agents. The agents (a) and (b) are
different.
In principle, agents (a) and (b) can be applied simultaneously or
successively, whereby successive application is exemplary.
The best results were obtained when agent (a) was applied to the
keratin materials as a pretreatment agent and then agent (b) was
applied as a colorant.
Therefore, a method for dyeing keratinous material, in particular
human hair, including the following steps in the order given is
suitable: in a first step, applying an agent (a) to the keratinous
material, wherein the agent (a) contains at least one organic
silicon compound selected from silanes having one, two or three
silicon atoms, wherein the organic silicon compound includes one or
more hydroxyl groups and/or hydrolysable groups per molecule, and
wherein the agent (a) further contains at least one
oligoalkylsiloxane, and in a second step, applying an agent (b) to
the keratinous material, the agent (b) including at least one
colorant compound selected from the group including pigments and/or
direct dyes.
The agents (a), and (b) are particularly suitably applied within
one and the same dyeing process, which means that there is a period
of a maximum of several hours between the application of agents (a)
and (b).
In a further exemplary embodiment, a method as contemplated herein
first the agent (a) is applied, and then the agent (b) is applied,
the time between the application of the agents (a) and (b) being at
most about 24 hours, suitably at about most 12 hours and
particularly suitably at most about 6 hours.
Within the scope of the procedure as contemplated herein, the
keratin materials, in particular human hair, are first treated with
agent (a). Then the actual colorant (b)--which contains the
coloring compounds--is applied to the keratin materials.
Suitably, agent (a) itself does not contain colorants or coloring
compounds. A characteristic feature of the pretreatment agent (a)
is its content of at least one reactive organic silicon compound
and at least one oligoalkylsiloxane. The reactive organic silicon
compound(s) (a) functionalize the hair surface as soon as they meet
it. In this way a first, still uncolored film is formed. The rate
at which this film is formed in the dyeing process can be adjusted
to the optimum rate by adding the oligoalkylsiloxane to the agent
(a). In the second step of the process, a colorant (b) is now
applied to the hair. During application of the colorant (b), the
colorant compounds interact with the silane film and are thus bound
to the keratin materials. Here, the technical application
properties of the resulting dyeing can be further improved by
selecting the optimum process conditions.
In the context of a further form of execution, a procedure
including the following steps in the order indicated is
suitable.
(1) Application of agent (a) on the keratinous material,
(2) Allow the agent (a) to act for a period of from about 10
seconds to about 10 minutes, suitably from about 10 seconds to
about 5 minutes,
(3) if necessary, rinse the keratinous material with water,
(4) Application of agent (b) on the keratinous material,
(5) Allow the agent (b) to act for a period of from about 30
seconds to about 30 minutes, suitably from about 30 seconds to
about 10 minutes, and
(6) Rinse the keratinous material with water.
The rinsing of the keratinous material with water in steps (3) and
(6) of the process is understood, as contemplated herein, to mean
that only water is used for the rinsing process, without any other
agents other than agents (a) and (b).
In a first step (1), agent (a) is applied to the keratin materials,
especially human hair.
After application, the agent (a) can act on the keratin materials.
In this context, application times from about 10 seconds to about
10 minutes, suitably from about 20 seconds to about 5 minutes and
especially suitably from about 30 seconds to about 2 minutes on the
hair have proven to be particularly beneficial.
In a exemplary embodiment of the method as contemplated herein, the
agent (a) can now be rinsed from the keratin materials before the
agent (b) is applied to the hair in the subsequent step.
Dyeing's with also good wash fastness were obtained when agent (b)
was applied to the keratin materials which were still exposed to
agent (a).
In step (4), agent (b) is now applied to the keratin materials.
After application, let the agent (b) act on the hair.
The process as contemplated herein allows the production of
dyeing's with particularly good intensity and wash fastness even
with a short exposure time of agent (b). Application times from
about 10 seconds to about 10 minutes, suitably from about 20
seconds to about 5 minutes and most suitably from about 30 seconds
to about 3 minutes on the hair have proven to be particularly
beneficial.
In step (6), agent (b) (and any remaining agent (a)) is rinsed out
of the keratin material with water.
In the context of a further form of execution, a procedure
including the following steps in the order indicated is
suitable.
(1) Application of agent (a) on the keratinous material,
(2) Allow the agent (a) to act for a period of from about 10
seconds to about 10 minutes, suitably from about 10 seconds to
about 5 minutes,
(3) if necessary, rinse the keratinous material with water,
(4) Application of agent (b) on the keratinous material,
(5) Allow the agent (b) to act for a period of from about 30
seconds to about 30 minutes, suitably from about 30 seconds to
about 10 minutes, and
(6) Rinse the keratinous material with water.
In this embodiment, the sequence of steps (1) to (6) suitably takes
place within about 24 hours.
Multi-Component Packaging Unit (Kit-of-Parts)
Within the scope of the procedure as contemplated herein, agents
(a) and (b) are applied to the keratin materials, i.e., both agents
(a) and (b) are ready-to-use agents.
To increase user comfort, the user is suitably provided with all
required resources in the form of a multi-component packaging unit
(kit-of-parts).
A second subject matter of the present disclosure is therefore a
multi-component packaging unit (kit-of-parts) for coloring
keratinic material, comprehensively packaged separately from one
another. a first container including an agent (a), wherein the
agent (a) includes at least one organic silicon compound selected
from silanes having one, two or three silicon atoms, wherein the
organic silicon compound includes one or more hydroxyl groups
and/or hydrolysable groups per molecule, and wherein the agent (a)
further includes at least one oligoalkylsiloxane, and a second
container including an agent (b), the agent (b) including at least
one colorant compound selected from the group including pigments
and/or direct dyes.
The organic silicon compounds contained in agent (a) of the kit
correspond to the organic silicon compounds that were also used in
agent (a) of the method described above.
The oligoalkylsiloxanes contained in agent (a) of the kit
correspond to the oligoalkylsiloxanes that were also used in agent
(a) of the previously described process.
The colorant compounds from the group of pigments and/or direct
dyes contained in agent (b) of the kit correspond to the colorant
compounds from the group of pigments and/or direct dyes that were
also used in agent (b) of the previously described process.
A second subject of the present disclosure is therefore a
multi-component packaging unit (kit-of-parts) for coloring
keratinous material, comprehensively packaged separately from one
another. a first container including an agent (a), wherein the
agent (a) includes at least one organic silicon compound selected
from silanes having one, two or three silicon atoms, wherein the
organic silicon compound includes one or more hydroxyl groups
and/or hydrolysable groups per molecule, and wherein the agent (a)
further includes at least one oligoalkylsiloxane, wherein organic
silicon compound and oligoalkylsiloxane were disclosed in detail in
the description of the first subject matter of the present
disclosure a second container including an agent (b), the agent (b)
including at least one colorant compound selected from the group
including pigments and/or direct dyes, as disclosed in detail in
the description of the first subject matter of the present
disclosure.
The agent (a) contains with the organic silicon compound(s) a class
of highly reactive compounds which can undergo hydrolysis or
oligomerization and/or polymerization in the presence of water as
described above. Due to their high reactivity, these organic
silicon compounds form a film on the keratin material.
To prevent premature oligomerization or polymerization and to
control the polymerization rate, the agent (a) additionally
contains at least one oligoalkylsiloxane.
To avoid premature oligomerization or polymerization, it is of
considerable advantage to the user to prepare the ready-to-use
agent (a) only shortly before application.
In the context of a further embodiment, a multi-component packaging
unit (kit-of-parts) for coloring keratinic material is suitably
packaged separately from one another. a first container including
an agent (a1), wherein the agent (a1) includes at least one organic
silicon compound selected from silanes having one, two or three
silicon atoms, wherein the organic silicon compound includes one or
more hydroxyl groups and/or hydrolysable groups per molecule, and
wherein the agent (a1) further includes at least one
oligoalkylsiloxane, and a second container including an agent (a2),
the agent (2) including water, and a third container including an
agent (b), the agent (b) including at least one colorant compound
selected from the group including pigments and/or direct dyes.
To provide a formulation that is as stable as possible during
storage, the agent (a1) itself is suitably packaged with low or no
water.
A kit-of-parts packaging unit as contemplated herein the agent
(a1)--based on the total weight of the agent (a1)--contains a water
content of from about 0.001 to about 10.0% by weight, suitably from
about 0.5 to about 9.0% by weight, more suitably from about 1.0 to
about 8.0% by weight and very particularly suitably from about 1.5
to about 7.0% by weight.
The agent (a2) contains water. In a exemplary embodiment, a
multi-component packaging unit (kit-of-parts) as contemplated
herein the agent (a2)--based on the total weight of the agent
(a2)--has a water content of from about 15 to about 100% by weight,
suitably from about 35 to about 100% by weight, more suitably from
about 55 to about 100% by weight, still more suitably from about 65
to about 100% by weight and very particularly suitably from about
75 to about 100% by weight.
Within this version, the ready-to-use agent (a) is now produced by
mixing agents (a1) and (a2).
For example, the user can first mix or shake the agent (a1)
containing the organic silicon compound(s) with the
water-containing agent (a2). The user can now apply this mixture of
(a1) and (a2) to the keratin materials--either directly after their
production or after a short reaction time of from about 10 seconds
to about 20 minutes. Afterwards, the user can apply agent (b) as
described above.
In a exemplary embodiment, a multicomponent packaging unit
(kit-of-parts) as contemplated herein the agent (a1)
contains--based on the total weight of the agent (a1)--one or more
organic silicon compounds of the formula (I) and/or (II) in a total
amount of from about 1.0 to about 35.0% by weight, suitably from
about 3.0 to about 25.0% by weight, more suitably from about 6.0 to
about 20.0% by weight and very particularly suitably from about 9.0
to about 15.0% by weight.
In a exemplary embodiment, a multicomponent packaging unit
(kit-of-parts) as contemplated herein the agent (a1)
contains--based on the total weight of the agent (a1)--one or more
organic silicon compounds of the formula (IV) in a total amount of
from about 1.0 to about 80.0% by weight, suitably from about 10.0
to about 70.0% by weight, more suitably from about 20.0 to about
60.0% by weight and very particularly suitably from about 30.0 to
about 60.0% by weight.
In a exemplary embodiment, a multicomponent packaging unit
(kit-of-parts) as contemplated herein the agent (a1)
contains--based on the total weight of the agent (a1)--one or more
oligoalkylsiloxanes in a total amount of from about 5.0 to about
50.0% by weight, suitably from about 10.0 to about 45.0% by weight,
more suitably from about 15.0 to about 40.0% by weight and very
particularly suitably from about 20.0 to about 35.0% by weight.
With respect to the other exemplary embodiments of the
multi-component packaging unit as contemplated herein, the same
applies mutatis mutandis to the procedure as contemplated
herein.
EXAMPLES
1. Formulations
The following formulations were produced:
Pretreatment Agent (a)
TABLE-US-00001 (a1E) (a1V1) (a1V2) Present Agent (a1) Comparison
Comparison disclosure (3-Aminopropyl)triethoxysilan 13.3 g 13.3 g
13.3 g Methyltrimethoxysilane 46.7 g 46.7 g 46.7 g
Hexamethyldisiloxane -- -- 33.3 g Water 40.0 g -- 6.7 g Agent (a2)
(a2) Ammonia/citric acid ad pH 9.5 Water 100 g
Colorant (b)
TABLE-US-00002 (b) Acid Violet 43 2.0 g PVP K 30 (Ashland, ISP, 4.5
g Polyvinylpyrrolidone) Dermacryl 79 (Akzo Nobel, 4.5 g
Acrylates/Octylacrylamide Copolymer, CAS-Nr. 129702-02-9) Ammonia
(25% aqueous solution) ad pH 10 Water ad 100 g
2. Storage Test
5 g each of the agent (a1V1), (a1V2) and (a1E) were filled into a
glass bottle directly after preparation. Each glass bottle was left
open for 1 hour. Then, each glass bottle was sealed and stored at
25.degree. C. for 10 weeks.
TABLE-US-00003 (a1V1) (a1V2) (a1E) Present Comparison Comparison
disclosure 10 Weeks, streaky, jelly streaky, slightly clear
solution 25.degree. C. gel-like
3. Application
To prepare the ready-to-use pretreatment agent (a), the indicated
amount of stored agent (a1V1), (a1V2) and (a1E), respectively, were
mixed with the indicated amount of agent (a2) with shaking.
Afterwards the agent (a) was left to stand for 15 minutes. The
agent (a) is the ready-to-use agent.
One strand of hair (Kerling, Euronatural hair white) was dipped
into the medium (a) and left in it for 1 minute. Afterwards, excess
product (a) was stripped from each strand of hair. Each strand of
hair was washed out with water. Excess water was scraped off each
strand of hair.
Subsequently, the hair strands were each dipped in the agent (b)
and left in it for 1 minute. Afterwards, excess agent (b) was
stripped from each strand of hair. Each strand of hair was dried
and visually evaluated. Then, each hair strand was thoroughly
washed (1 min) with water, dried, and visually assessed again.
TABLE-US-00004 Specimen 1 2 3 Agent (a1), (a1V1) (a1V2) (a1E)
stored 10 weeks, 8.4 g 5 g 8.4 g 25.degree. C. Agent (a2) 91.6 g 95
g 91.6 g Agent (b) (b) (b) (b) Staining before faint violet +
violet ++ violet +++ washing out Staining after almost faint violet
+++ washing out uncolored - violet + Color intensity: - = uncolored
+ = low ++ = average +++ = very good
While at least one exemplary embodiment has been presented in the
foregoing detailed description, it should be appreciated that a
vast number of variations exist. It should also be appreciated that
the exemplary embodiment or exemplary embodiments are only
examples, and are not intended to limit the scope, applicability,
or configuration of the various embodiments in any way. Rather, the
foregoing detailed description will provide those skilled in the
art with a convenient road map for implementing an exemplary
embodiment as contemplated herein. It being understood that various
changes may be made in the function and arrangement of elements
described in an exemplary embodiment without departing from the
scope of the various embodiments as set forth in the appended
claims.
* * * * *